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Review

pubs.acs.org/CR

Potassium−Sodium Niobate Lead-Free Piezoelectric Materials: Past,


Present, and Future of Phase Boundaries
Jiagang Wu,* Dingquan Xiao, and Jianguo Zhu
Department of Materials Science, Sichuan University, Chengdu 610064, China
4.5.9. Sintering Aids and Sintering Atmos-
phere 2580
4.6. Extrinsic Factors 2581
4.6.1. Density vs Electrical Properties 2581
4.6.2. Grain Morphology vs Electrical Proper-
ties 2582
4.6.3. Domain Structure vs Electrical Proper-
ties 2582
CONTENTS 5. Relationship between Phase Boundaries and
Piezoelectricity 2583
1. Introduction 2559 6. Applications of KNN-Based Materials 2584
2. Background of Phase Boundaries 2562 6.1. Piezoelectric Energy Harvesting 2584
3. Characterization Tools of Phase Boundaries 2563 6.2. Piezoelectric Actuator 2584
3.1. High-Resolution Synchrotron X-ray Diffrac- 7. Outlook and Future Work 2585
tion 2564 7.1. Designing New Phase Boundaries 2585
3.2. Neutron Diffraction 2564 7.2. Analyzing Phase Compositions 2585
3.3. Transmission Electron Microscopy 2564 7.3. Physical Origin of High Piezoelectricity 2585
3.4. Spectroscopic Techniques 2564 7.4. Intrinsic Characteristics of Phase Boundaries 2586
3.4.1. Raman Spectroscopy 2564 7.5. Investigating the Stability of Piezoelectricity 2586
3.4.2. Infrared Spectroscopy 2565 7.6. Other Issues 2586
3.5. Theoretical Methods 2565 8. Conclusions 2586
3.6. Combined Tools 2565 Author Information 2586
4. Type and Construction of Phase Boundaries 2566 Corresponding Author 2586
4.1. Orthorhombic−Tetragonal Phase Bounda- Notes 2586
ries 2566 Biographies 2586
4.1.1. Li+ Substitution 2566 Acknowledgments 2586
4.1.2. Li+ and Sb5+ Substitution 2567 References 2587
4.1.3. Li+ and Ta5+ Substitution 2567
4.1.4. Li+, Sb5+, and Ta5+ Substitution 2568
4.1.5. Addition of ABO3 2568 1. INTRODUCTION
4.1.6. Addition of ABO3 Multicomponents 2569
4.1.7. Ratio of K/Na 2570 High-performance piezoceramics are some of the most
4.1.8. Other Ions 2570 important and widely used materials, and as such research
4.2. Rhombohedral−Orthorhombic Phase Boun- into this topic is at the forefront of high-technology advanced
daries 2570 materials.1−19 Since the 1950s, (PbZr1−xTixO3, PZT)-based
4.3. Rhombohedral−Tetragonal Phase Bounda- ceramics have been given much attention due to their excellent
ries 2572 piezoelectric constants (d33 ≈ 200−750 pC/N) and high Curie
4.4. Dopant Engineering 2574 temperatures (TC = 180−320 °C) (see Figure 1) and are
4.4.1. Doping with Equipollent Metals 2574 currently applied in many electronic devices (e.g., sensors,
4.4.2. Doping with Aliovalent Metals 2574 actuators, ultrasound transducers, etc.).4,5,7−11,20,21 However,
4.5. Supplementary Tools 2575 the lead content (∼60 wt %) of PZT raises environmental
4.5.1. Sintering Temperature 2576 concerns during their preparation, process, and even dis-
4.5.2. Reactive Template Grain Growth Meth- posal.4,5,7−11,20,21 For maintaining socially sustainable develop-
od 2576 ment, regions and countries have put a great deal of effort into
4.5.3. Spark-Plasma Sintering 2576 the research and development (R&D) of lead-free piezoelectric
4.5.4. Nonstoichiometry 2577 materials, and moreover, the related laws and regulations have
4.5.5. Two-Step Sintering 2577 been legislated or improved.22−34 For example, the European
4.5.6. Single Crystals 2578 Union passed the Restriction of Hazardous Substances (RoHS)
4.5.7. Thin Films 2580
4.5.8. Poling Conditions 2580 Received: December 1, 2014
Published: March 20, 2015

© 2015 American Chemical Society 2559 DOI: 10.1021/cr5006809


Chem. Rev. 2015, 115, 2559−2595
Chemical Reviews Review

Figure 1. d33 and TC of PZT-based ceramics. Figure 2. Publications on lead-free piezoceramics in refereed journals
for the time range from 2004 to 2014 (collected from ISI Web of
law in 2003, the “Household Electronic Products Recycling Science with the keywords “lead-free” and “piezoelectric”).
Law” was passed in Japan, and the “Electronic Information
Product Pollution Control Management Regulation” was statistical results indicate that alkali niobium-based materials
established in China in 2006. Although the lead content of have received a great amount of attention.12,90−285 To better
piezoelectric devices and some capacitors is currently exempted understand this situation, we counted the percentage of the
due to related technical questions, the validity of this exemption publications according to the data of Figure 2, as plotted in
treaty will expire in July 2016. As a result, the R&D of lead-free Figure 3a and 3b. Publications on alkali niobium materials make
piezoelectrics has become urgent under current international
legislature.1−3,14−19,35−285
Among these lead-free candidates, (K,Na)NbO3 (KNN) has
become one of the most extensively investigated piezoelectric
systems in the past 10 years due to its large d33 and high
TC.12,17,97,101,102,104,106 Recently, a number of countries have
invested considerable manpower and financial resources into
the study of KNN-based piezoelectrics, and some significant
breakthroughs have been achieved.12,101,105−118,166,256,260,262
For example, Satio et al. observed a large d33 value (∼416
pC/N) in (K,Na,Li)(Nb,Ta,Sb)O3-textured ceramics fabricated Figure 3. (a) Publications on alkali niobium-based and lead-free
using reactive templated grain growth (RTGG) methods.12 In piezoceramics in refereed journals for the time range from 2004 to
the meantime, Cross commented that Satio’s work may allow 2014; (b) publications on lead-free piezoceramics with phase
us to be “Lead-free at last”.100 Guo et al.,101,102 meanwhile, also boundary construction and others.
observed enhanced piezoelectricity (d33 = 200−235 pC/N) in
KNN ceramics by doping LiNbO3 or LiTaO3 using conven-
tional solid-state methods. In these studies, their d33 values can up ∼43.85% of those on lead-free piezoelectrics, and moreover,
be promoted to be several times that of a pure KNN ceramic,3 those concerned with the construction of phase boundaries
and the involved phase boundaries play a large part in their comprise 53.27%. As a result, phase boundaries play an
improved piezoelectricity (refs 12, 16−18, 97, 101, 105−119, important role in the development of alkali niobium lead-free
166, 251, 256, 260, and 262). In 2014, we developed new piezoelectrics as a whole. In the past, the “morphotropic phase
KNN-based material systems with large piezoelectricity (d33 ≈ boundary” was also used to realize a major breakthrough in the
490 pC/N) by designing new phase boundaries consisiting of study of the piezoelectric activity of PZT.4,5 Generally speaking,
rhombohedral and tetragonal (R−T) phases;106 moreover, this the piezoelectric activity of KNN-based ceramics is still inferior
material was able to demonstrate both a large d33 and a high TC to that of most PZT materials (see Figure 1), and thus, further
through refining of its composition,106−118,256,260 further breakthroughs must be achieved by extensively replacing lead-
increasing research interest in KNN-based piezoelectrics. based materials in some applications. As mentioned above, the
Figure 2 displays statistics related to refereed publications on construction of phase boundaries will be key to realizing the
lead-free piezoceramics from 2004 to 2014 using the keywords enhanced piezoelectricity of KNN compared to PZT; thus, it is
“lead-free” and “piezoelectric”. We classified the referenced necessary to review the developments of phase boundaries in
publications according to the keywords “lead-free piezo- the field of KNN-based materials for further promotion of the
electric”, “alkali niobium-based”, and “construction of alkali piezoelectric activity and to guide our studies.
niobium-based materials”, as shown in Figure 2. There is a In the past 10 years, researchers have reviewed the advances
gradually increasing trend in the number of publications of KNN-based materials from different view-
concerning alkali niobium-based materials, among which the points,16−19,96−98,103−105,266,267 greatly accelerating research
construction of phase boundaries has become a prominent tool progress.16−19,103−120 For example, the relationships between
for the improvement of their electrical properties. The microstructure (domain wall) and properties concerning lead-
2560 DOI: 10.1021/cr5006809
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Figure 4. Diagram summarizing the topics in this review.

free piezoelectric materials were first reviewed by Damjanovic above, the improved piezoelectricity of such a material should
et al.,96 and Shrout and Zhang comprehensively analyzed the be largely due to the construction of phase boundaries. As a
difference between KNN and PZT.18 Rodel et al. reviewed the result, we focused our attention on the design and construction
phase structure and electrical properties of KNN-based of different phase boundaries (e.g., rhombohedral−orthorhom-
materials by analyzing different processing techniques and bic (R−O), orthorhombic−tetragonal (O−T), rhombohedral−
chemical modifications,17 and the related applications of lead- tetragonal (R−T), etc.) in potassium−sodium niobate
free piezoelectrics have been recently summarized.120 Panda materials, the relationships between phase boundaries and
reviewed the effects of additives on the electrical properties of piezoelectricity are particularly emphasized, and some sugges-
KNN-based materials.103 In 2009, Xiao et al. reviewed the tions have been addressed.
composition design and property modification of KNN- and This review has been organized as shown in Figure 4. In the
BNT-based ceramics by considering their recent publica- first part, we give a general introduction to the background and
tions.104 Li et al. introduced the developments of lead-free
characterization methods of phase boundaries for elucidating
piezoelectric materials in China, and their preparation and
the phase structure−performance relationships. In the second
electric properties were emphasized.266 More recently, the
phase structure (e.g., orthorhombic−tetragonal), property part, we focus on the design and construction of phase
enhancement approaches, and sintering processes as well as boundaries in potassium−sodium niobate materials by chemical
some promising applications of KNN-based materials were modifications. Special emphasis is placed on the composition-
reviewed by Li et al.105 Finally, Priya et al. published a induced phase boundaries by analyzing the chemical
monograph on lead-free piezoelectric materials in 2012.267 In modifications in detail, and dopant engineering is also
most reviews, the phase structure mainly refers to the mentioned. It is worth noting that we observed the largest
orthorhombic−tetragonal phase boundary or the KNN-based piezoelectricity ever reported by developing new phase
materials are only reviewed as a minor part of a larger field or boundaries. In addition, supporting tools for further enhancing
from different viewpoints. In addition, there are few systematic piezoelectricity are also discussed in this review. In the third
reviews on the developments of phase boundaries in part, we illuminate the relationships between phase boundaries
potassium−sodium−niobate-based materials. As mentioned and piezoelectric activity, discuss some existing challenges,
2561 DOI: 10.1021/cr5006809
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Chemical Reviews Review

Figure 5. Intrinsic difference between (a) polymorphic phase transition (PPT) and (b) morphotropic phase boundary (MPB)17,200

Figure 6. Phase transition behavior of K0.48Na0.52Nb0.98Sb0.02O3 ceramics.

suggest possible methods for further improving piezoelectricity, kind of phase boundary is thought to be an MPB,286 which is
and provide some conclusions. only dependent on the compositions and independent of the
measurement temperatures, as shown in Figure 5b. However,
2. BACKGROUND OF PHASE BOUNDARIES the phase boundaries (e.g., R−O and O−T) in KNN-based
The modification of phase boundaries is a powerful tool for the materials were considered as the intrinsic characteristics of
promotion of electrical properties of piezoelectric materials, i.e., “polymorphic phase transition (PPT)”,120,131 and their
the involved phase boundaries and their corresponding types electrical properties are very sensitive to not only the
are largely responsible for the enhancement in piezoelectric compositions but also the temperatures (see Figure 5a).
activity, regardless of whether a material is lead based or lead According to advances in KNN materials, there are three
free (refs 4, 5, 11, 16−19, 35, 70, 76, 96−120, and 286−315). A kinds of existing phase transitions (Figure 6), corresponding to
number of experimental (refs 70, 287−298, 300, 301, 304, 305, the rhombohedral−orthorhombic phase transition temperature
307, 309, 311, and 312) and theoretical methods (refs 20, 299, (TR−O), the orthorhombic−tetragonal phase transition temper-
301, 303, 306, 308, 310, and 313−315) have been used to ature (TO−T), and the rhombohedral−tetragonal phase
investigate the relationships between phase boundaries and the transition temperature (TR−T).17,18 Figure 6 shows the phase
piezoelectric activity of a material. It is generally accepted that a transition behavior of K0.48Na0.52Nb0.98Sb0.02O3 ceramics,
high degree of alignments of ferroelectric dipoles can be driven measured at −150−550 °C and f = 10 kHz. One can see that
by a large amount of thermodynamically equivalent states TR−O, TO−T, and TC are clearly shown according to the
under a driving electric field during the poling process, easily temperature dependence of the corresponding dielectric peaks.
generating enhanced electrical properties.70,286−311 The con- At room temperature, the R−O or O−T phase boundary could
struction of morphotropic phase boundaries (MPB) in PZT is be formed in KNN by shifting TR−O or TO−T to room
considered a classic case in the field of piezoelectric temperature using additives such as LiNbO3,101,160,161,166−178
materials,286,289,293,305 wherein the crystal structure changes Li(Ta/Sb)O3,102,133,163−165,182−203 Li(Ta−Sb)-
abruptly and the piezoelectricity is maximized for compositions O3,132,151,156,157,204,206−214 (Bi0.5A0.5)TiO3 (A = Na+, K+,
at MPBs.286,289,293,305 For example, enhanced piezoelectric Li+),215−218 BiBO3 (B = Al3+, Fe3+, Sc3+),225,230,252 SrZrO3,138
activity was observed in PZT materials with a Zr/Ti ratio of Sb5+,251 BaZrO3,397 Ta5+,254 etc. In contrast, the phase
52:48 owing to the structural changes going from tetragonal to boundary corresponding to R−O or O−T possesses the PPT
rhombohedral via an intermediary monoclinic phase;292 this characteristic,97,155,251,264,265 depending on not only the
2562 DOI: 10.1021/cr5006809
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Figure 7. d33 vs TC of (a) lead-based and (b) lead-free materials, derived from a number of publications.4,5,16−19,35,50,59,68,97,101,102,106,120,315−339

compositions but also the temperatures, as shown in Figure 5a. boundaries (e.g., R−O, R−T, or O−T). Although a larger d33
Such a phase boundary is obviously different from that of PZT can usually be realized in BaTiO3-based materials, a low TC is a
(see Figure 5b). Regardless of the presence of MPB or PPT fatal shortcoming for high-temperature practical applica-
characteristics, the polarization of a piezomaterial can be more tions.35−38,40−43,45,50,53,59,84 However, such materials are
easily rotated among different symmetries when the composi- suitable to prepare actuators with usage temperatures below
tions are located at the phase boundaries, inducing an 100 ◦C. Similar to BaTiO3-based materials, the low “depoling
enhancement in dielectric and piezoelectric properties. temperature” hinders the practical applications of
However, recent advances indicate that there is a limited Bi0.5Na0.5TiO3-based materials,63−73 and a large strain com-
improvement in the d33 values for KNN materials with O−T or parable or even superior to PZT has been developed by Rödel
R−O phase boundaries,90−105,250−252 which is also inferior to and Jo et al.66−68,73−77 More interestingly, we can see from
most PZT ceramics5 or even textured KNN.12 As a result, the Figure 7b that KNN-based materials have wider d33 and TC
formation of R−T boundaries that are similar to PZT may distributions (e.g., d33 = 171−490 pC/N, TC = 178−475 °C)
become necessary to further enhance the piezoelectric activity (refs 12, 17, 97, 101, 102, 104, 106−118, 166, 277, 284, and
of KNN, because the easy rotations of polarization axes can be 285), which is determined by the phase boundary types and the
induced in compositions near such a phase boun- composition itself. In particular, we achieved a breakthrough in
dary.11,35,70,76,106−117 In addition, we recently confirmed this the piezoelectricity of KNN-based ceramics by forming new R−
assumption in potassium−sodium niobate piezoceramics by T phase boundaries.106−118 As a result, the construction of new
experimental methods,106−116 and a larger d33 value has been phase boundaries has become an efficient way to further
attained by constructing R−T phase boundaries.106−112 If the enhance the piezoelectricity of KNN materials, narrowing the
R−T phase boundary of KNN is expected to form, it is gap between lead-free and lead-based materials.
necessary to concurrently move their TR−O and TO−T values
close to room temperature by choosing two or more 3. CHARACTERIZATION TOOLS OF PHASE
additives, 1 0 6 − 1 1 6 , 2 5 5 − 2 6 3 such as Ta and Sb and BOUNDARIES
Bi0.5(Na0.82K0.18)0.5ZrO3,106 Sb and Bi0.5(Na0.82K0.18)0.5ZrO3,107 Although the phase boundary has some incomparable
BaZrO3 and Bi0.5Na0.5TiO3,255 Sb and BaZrO3,256 Sb and advantages, it is very difficult to know the actual phase
LiTaO3 and BaZrO3,257 LiSbO3 and BaZrO3,258 Sb and compositions and types of phase boundaries in a material.
Bi0.5Na0.5TiO3,259 Sb and (Bi,Na,K,Li)ZrO3,260 Researchers have invested much effort in exploring the origin of
Bi0.5(Na0.7K0.2Li0.1)0.5ZrO3 and B0.5Na0.5TiO3,261 etc. As a result, ultrahigh piezoelectricity in lead-based perovskite oxides with
it is possible to develop high-performance KNN-based MPBs by analyzing the phase constituents using experimental
materials by the application of new ideas. and theoretical methods.65,287,298,323,341−391 Previously, it was
The phase boundaries of a material can be driven by its thought that 14 possible equivalent polarization vectors
chemical composition or other factors (refs 4, 10, 35, 50, 59, 68, determine the ultrahigh piezoelectric activity in MPB lead-
97, 101, 102, 106, and 316−340) that determine the electrical based materials.341 However, it was observed by means of high-
properties. Figure 7a and 7b shows the d33 vs TC of lead-based resolution X-ray powder diffraction measurements that
(e.g., PZT, 4,5,316 Pb(Ni 1/3 Nb 2/3 )O 3 −PbTiO 3 (PNN− intermediate phases may coexist in the R−T phase boundary
PbTiO3),317−321 BiScO3−PbTiO3 (BSPT),322−332 and relaxor- of PZT,293,342,343,347 and an intermediate phase induces an
PbTiO3333−340) and lead-free (e.g., ultrahigh piezoelectricity. In particular, the monoclinic (M)
BaTiO 3 , 35−38,40−43,45,50,53,59,84 Bi 0.5 Na 0.5 TiO 3 , 63−73 and phase, as an intermediate phase of MPB, is considered to
(K,Na)NbO390−265) materials with compositions at the phase effectively enhance the piezoelectricity of PZT.342 Since an M
boundaries, wherein all data were derived from the references. phase was found in MPB-PZT,343 much attention has been
A giant d33 value was observed in PNN-based and relaxor PT given to the determination of its phase compositions. Some
single crystals with an MPB,317−321,333−340 while PZT-based powerful tools can identify the existence of the intermediate
materials possess a wide d33 distribution,4,5,316 which is sensitive phases and thus explain the physical origin of enhanced
to the doping elements, as shown in Figure 7a. Figure 7b piezoelectricity, including high-resolution synchrotron X-ray
displays the d33 and TC values of BaTiO3-, Bi0.5Na0.5TiO3-, and powder diffraction,293,298,342,344 neutron diffraction,359,360 spec-
K0.50Na0.50NbO3-based lead-free ceramics with different phase troscopic techniques (i.e., Raman346,347,367−369 and infrared
2563 DOI: 10.1021/cr5006809
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Chemical Reviews Review

spectroscopies369,370), dielectric measurements,350 transmission phase transitions from a nonpolar to a ferroelectric state.365 Yao
electron microscopy (TEM),361−366 theoretical studies,354,355 et al.366 reported that the ferroelectric domains and local
and Rietveld studies.376 In addition, two or more methods are structures of Bi0.5Na0.5TiO3−BaTiO3 single crystals could be
often used together to clarify the phase compositions near the identified by TEM, the size of polar nanoregions were refined,
phase boundary regions of a material.371−375 In this section, we and the tetragonal phase volume fraction was shown to increase
briefly introduce the methods of characterization of the phase as the BT content increased, indicating that both polarization
compositions in KNN-based materials. rotation and polarization extension lead to large electric-field-
3.1. High-Resolution Synchrotron X-ray induced strains in materials with MPBs.366 Recently, Zuo et
Diffraction298,342,343,356−358 al.268 discussed the origin of the high piezoelectric activity in
(Na0.52K0.48−x)(Nb0.92−xSb0.08)O3−xLiTaO3 ceramics by char-
Structural information on lead-based piezoelectrics with MPBs acterization of the domain evolutions using TEM, indicating
can be obtained by high-resolution synchrotron X-ray that the nanodomain morphologies are responsible for their
diffraction.293,298,342,344,356−358 For example, Noheda et al.342 enhanced piezoelectricity.
found that a monoclinic phase bridges tetragonal and In the past, the relationships between grain size and domain
rhombohedral regions of PbZr0.52Ti0.48O3 using high-resolution of ferroelectric materials were extensively investigated using
synchrotron X-ray powder diffraction measurements. In 2000, TEM in order to understand the size effect on their electrical
Noheda et al.345 also established the stability region of three properties.377−383 It is well known that the domain size of
phases (e.g., monoclinic, tetragonal, and rhombohedral phases) ferroelectric materials is closely related to the corresponding
in PbZr1−xTixO3 (0.42 ≤ x ≤ 0.52) according to data from grain size, as shown here.382,383
high-resolution synchrotron X-ray powder diffraction measure-
ments. These results indicate that PbZr1−xTixO3 (0.46 ≤ x ≤ Domain Size ≈ (Grain Size)m (1)
0.51) ceramics possess a stable monoclinic phase when
measured at 20 K, the phase composition region becomes According to eq 1, the grain size of the samples used for
narrower and narrower with increasing temperatures, and the TEM observation can strongly affect their domain size,382 that
role of such a monoclinic phase in the ultrahigh piezoelectricity is, the prepared samples are in agreement with the bulk domain
of the materials was especially emphasized.293 In addition, this structures. As a result, it becomes critical to accurately
method could also be used to detect the phase compositions of characterize the domains to evaluate the underlying physical
other material systems.298,358 An orthorhombic phase in mechanisms. To attain useful information about material
PbZn1−xTixO3 and Pb(Zn1/3Nb2/3)O3−PbTiO3 systems was structure and properties, TEM becomes an indispensable
identified by high-resolution synchrotron X-ray diffraction,298 tool. However, the size effects of ferroelectric materials
and a monoclinic phase (Cm) of 0.65Pb(Mg1/3Nb2/3)O3− presumably play a part in the TEM observations of domains,
0.35PbTiO3 was also confirmed.358 since the TEM samples are quite thin. Therefore, the sample
preparation technique is very important for TEM analysis in
3.2. Neutron Diffraction359,360
order to gain real insight into a material’s structure.384 It is
Neutron diffraction allows the atomic and/or magnetic usually very challenging to prepare a suitable sample of
structure of a material to be determined by neutron scattering, polycrystalline ceramics for TEM since some additional cracks
and this technique has been used to evaluate the symmetry of a and artifacts may be introduced during the sample prepara-
material.359,360 For example, neutron diffraction methods can tion.384 In addition to the TEM observation of domains, other
identify the symmetry of Pb(Zn1/3Nb2/3)O3−9%PbTiO3 with tools (scanning electron microscopy,269 piezoresponse force
an MPB, showing that a new polarization rotation line Mc# microscopy,270,271 etc.) should also be used to further confirm
(the orthorhombic−monoclinic line) coexists with rhombohe- the domain structure and to avoid artificial information. As a
dral and tetragonal phases.359 In addition, in situ neutron result, TEM can directly characterize domain structure and
diffraction experiments show that the varied coherence lengths morphologies, and the size effects should be given special
of polar nanoregions and internal stresses induced by domain attention in the observation of domains.
switching are responsible for different d33 values in textured and 3.4. Spectroscopic Techniques
polycrystalline 0.93Bi0.5Na0.5TiO3−0.07BaTiO3 ceramics.360
Spectroscopy is used to investigate the interactions between a
3.3. Transmission Electron Microscopy268,270,378
material and radiated energy;342,347,367−370 thereby, the phase
In 1931, Max Knoll and Ernst Ruska invented the first transitions of a material can be analyzed by spectroscopic
transmission electron microscope (TEM), allowing the techniques including Raman and infrared spectroscopies.367−370
structural information on ferroelectric materials to be directly 3.4.1. Raman Spectroscopy. Raman spectroscopy is used
characterized.268,361−366 For example, both orthorhombic− to characterize vibrational, rotational, and other low-frequency
orthorhombic and paraelectric−ferroelectric phase transitions modes in a material and can also identify the phase structure of
in SrBi4Ti4O15 have been directly observed by TEM.363 Randall a material.346,347 In 2000, Souza Filho et al. confirmed the MPB
et al.364 identified the differences between domain structure and consisting of tetragonal and monoclinic phases 346 in
symmetry of (1−x)BiScO3−xPbTiO3 materials using TEM, PbZr0.52Ti0.48O3 by Raman spectroscopy with the frequency
clearly showing the domain structures with R and T mixed and temperature of lattice modes.347
phases. In addition, the domain structure evolutions under an Confocal Raman microscopy can allow high-resolution
applied electric field were characterized in situ in (Bi1/2Na1/2)- chemical mapping of 2D or 3D materials. Recently, confocal
TiO3−BaTiO3−(K0.5Na0.5)NbO3 ceramics using TEM.365 This Raman microscopy (CRM) coupled with atomic force
result indicates that the domain structure cannot be clearly microscopy has been used to observe the domains of KNN-
observed when an electric field is retrieved, while a lamellar based materials.272,273 For example, Rubio-Marcos et al.
domain structure can be driven by an alternating electric field, identified the spatially resolved structure of the ferroelectric
graphically showing the involvement of electric field-induced domains in (K,Na)NbO3-based ceramics by confocal Raman
2564 DOI: 10.1021/cr5006809
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Figure 8. Possible chemical modifications of (K,Na)+ and Nb5+ sites in (K,Na)NbO3.

microscopy, where the characteristics of domain walls and Although theoretical methods can further guide experimental
structure−piezoelectricity correlation were clearly addressed.272 studies, there are also limitations inherent in some methods.
3.4.2. Infrared Spectroscopy. Infrared spectroscopy uses Most theoretical methods are only capable of modeling realistic
radiation from the infrared region of the electromagnetic systems,385,386 and the final results are also strongly dependent
spectrum, covering a range of techniques based on absorption on different simulated methods.387−389 For example, simu-
spectroscopy. It is well known that the onset of ferroelectric lations of the domain structures of ultrathin ferroelectric films
states can cause a change of infrared vibrational frequencies have mainly focused on conventional perovskite ferroelectrics
owing to its temperature-dependent phase transitions and thus (e.g., BaTiO3,390 PbTiO3,391 etc.). In these studies, only a few
can be used to characterize their phase transitions.369,370 For simple factors (e.g., boundary conditions, external electrical,
example, Araujo et al.369 showed that monoclinic → tetragonal and mechanical loads) were considered,390,391 while treatment
phase transitions in PbZr0.51Ti0.49O3 occur at 237 K by infrared of complicated situations and the detailed physics of the surface
spectroscopy, confirming this technique as a useful tool to and interface (i.e., octahedral rotation, magnetic ordering, other
analyze phase transitions. The monoclinic → tetragonal phase degrees of freedom) was seriously flawed. In addition,
transitions in PbZr0.50Ti0.50O3 can be confirmed by infrared theoretical methods have so far been unable to model the
spectroscopy with different measurement temperatures, and the true dynamics of the domain structures of ultrathin ferroelectric
obvious differences in higher frequency ν1-(Ti−O) and ν1-(Zr− films.385 As a result, satisfactory simulation of broad and
O) modes can show the structural changes in monoclinic → complicated systems will require further development of
computational methods,385 and special attention should be
tetragonal phases.370
given to the limitations of theoretical methods on the whole.
3.5. Theoretical Methods274−276,287,355,364,365,385−391
3.6. Combined Tools323,371−375
Theoretical methods rely on the creation of hypothetical
It is usually difficult to identify the phase compositions of a
models of materials. Such methods can predict the underlying
material using only one tool; thus, multiple techniques should
physical mechanisms of enhanced electrical properties well,
be used to determine the actual phase compositions.323,371−375
effectively supporting experimental results. In the past, In the past, combined tools have been used to identify the
theoretical methods have also been used to explain the origin phase structures of lead-based and lead-free materials.323,372−375
of ultrahigh piezoelectricity of lead-based materials with an For example, both variable-temperature transmission electron
MPB, such as a first-principle study by Fu and Cohen,287 and microscopy and dielectric measurements were used to
higher-order Devonshire theory studies by Vanderbilt and characterize the phase compositions of (1−x)BiScO3-xPbTiO3
Cohen.355 Fu et al. also reported that the large piezoelectricity single crystals in which x = 0.64.323 Schonau et al. studied the
in BaTiO3 is driven by the polarization rotation induced by an phase compositions and microstructural information on
external electric field using a first-principles study.287 In Pb(Zr1−xTix)O3 (0.40 ⩽ x ⩽ 0.475 and x = 0.55) materials
addition, some theoretical methods were also used to using three different tools (e.g., high-resolution synchrotron X-
investigate single-phase KNN materials.274−276 For example, ray diffraction, transmission electron microscopy, and electron
Zhu et al. indicated a combination of negative spherical- paramagnetic resonance) and found that a monoclinic phase is
aberration imaging using first-principles calculations and correlated to a miniaturization of its average domain
studied the atomic details across 60°/120° domain walls in structure.371 The phase compositions of (1−x)Pb(Ni1/3Nb2/3)-
(K0.46Na0.54)NbO3, providing an atomic basis for further O3−xPbTiO3 (x = 0.28−0.42) solid solutions were confirmed
investigation of the polarization mechanism.274 However, few by using both high-resolution synchrotron radiation X-ray
attempts have been made to predict the phase boundaries in diffraction and dielectric measurement, indicating that the
KNN materials. intermediate monoclinic phase exists between rhombohedral
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and tetragonal phases.372 Singh et al. investigated the In this section we mainly review the development of different
temperature-dependent phase structure in monoclinic Pb- types and constructions of phase boundaries in KNN materials,
(Zr0.525Ti0.475)O3 powders by Rietveld analysis of high- and some advice is provided for attaining piezoelectric activity
resolution synchrotron powder X-ray diffraction data in comparable to that of PZT. In addition, the detailed discussions
combination with its dielectric constant and planar electro- on how to construct phase boundaries by chemical
mechanical coupling coefficient.373 These powders, with a modifications are summarized here.
tetragonal phase, possess better piezoelectric activity than those 4.1. Orthorhombic−Tetragonal Phase Boundaries
with a monoclinic phase because of an anomalous softening of
the elastic modulus.373 Fu et al. studied the origin of enhanced The O−T phase boundary has become the most familiar one
piezoelectricity in (Na,K)(Nb,Sb)O3−LiTaO3−BaZrO3 ce- since a large breakthrough was achieved in KNN-based
ramics by combined tools consisting of high-resolution materials.12,101 The formation of the O−T phase boundary is
synchrotron X-ray data and dielectric measurements, showing one of the mosty hotly contested goals of research into KNN-
that an intermediate phase between R and T leads to a larger based materials (refs 101, 102, 132, 151−157, 159−168,
piezoelectricity.374 Maurya et al. addressed the origin of high 170−178, 182−197, 199−218, 220, 221, 224, and 229−247).
piezoelectricity in 0.93(Na0.5Bi0.5)TiO3−0.07BaTiO3 with an In 2004, the original breakthrough in its d33 value was achieved
MPB by comparative analyses of high-resolution transmission by varying O−T phase coexistence to or near room
electron microscopy and neutron diffraction, confirming that a temperature using Li, Ta, and Sb.12 For example, a high d33
pathway for polarization reorientation induced by an value of ∼416 pC/N was induced in KNN-based textured
intermediate monoclinic phase with nanotwins results in ceramics due to coexistence of O and T phases at room
enhanced piezoelectricity.375 As a result, multiple characteration temperature as well as the use of a new preparation technique
methods can compensate for the shortcomings of a single (e.g., RTGG),12 while at the same time LiNbO3- or LiTaO3-
method, thereby more accurately showing the phase modified KNN ceramics have attained enhanced piezoelectric
compositions of a material. activity by construction of the same phase boundary using
conventional solid-state methods.101,102 These original works
have greatly increased worldwide research interest in lead-free
4. TYPE AND CONSTRUCTION OF PHASE piezoelectrics, and thus, scientists have devoted much energy
BOUNDARIES into further promotion of the piezoelectric activity by
It is widely accepted that the piezoelectric activity of a material constructing O−T phase boundaries (refs 101, 102, 132,
can be promoted by forming phase boundaries by chemical 151−157, 159−168, 170−178, 182−197, 199−218, 220, 221,
modification (e.g., ion substitutions, binary or ternary solid 224, and 229−247). In the past, a number of successful
solutions, etc.).11,35,70,76,286−311 As far as KNN-based materials attempts were made to construct O−T phase boundaries in
are concerned, three kinds of phase boundaries (i.e., O−T, R− KNN-based ceramics in order to induce enhancement of its
O, and R−T) can be driven by doping with additives (refs piezoelectric activity, including ion substitutions (e.g., using
96−119, 131, 132, 136, 151, 152, 157, 161, 166, 169, 186−188, Li+,101,160,161,166−181 Li+/Sb5+,182−192 Li+/Ta5+,102,162,163,193−203
and 392−405), resulting in enhanced piezoelectricity. Li+/Sb5+ /Ta5+,12,156,204−214 etc.), solid solutions with other
Among these methods, chemical modifications are often used ABO 3 -type perovskites 215−228 or ABO 3 multicompo-
to tailor the phase compositions in the phase boundary regions nents,229−243 variation of the K/Na ratio,156,186,244−247 new
of KNN materials. To graphically show the chemical preparation techniques,109,125,165,166,175−177,190,196,210,245 etc. In
modifications of KNN materials, we depict the chemical this section we focus on reviewing the methods of construction
modifications of (K,Na)+ and Nb5+ sites in (K,Na)NbO3 in the of O−T phase boundaries.
Periodic Table (Figure 8). The colored boxes represent 4.1.1. Li+ Substitution. Ion substitution has become a
different chemical modifications of (K,Na)NbO3. Usually popular way to promote the piezoelectric properties of KNN-
monovalent cations (e.g., Li+101,162,166−173,392−394 and Ag+ ) based materials by the construction of O−T phase boundaries.
are able to easily substitute the (K,Na) site, and the Nb5+ site is It is now well known that Li+, Sb5+, and Ta5+ are the leading
often replaced by pentavalent cations (e.g., doping elements,12,102,156,160−163,166−214 which are able to
Ta5+ 102,162,163,193−203 and Sb5+ 182−190) because of their quickly shift the O−T phase boundary at or near room
identical valence and similar ionic radii. In addition, ABO3 temperature, resulting in an enhanced d33 value owing to the
can be constructed by combining (Mg, Ca, Sr, Ba, Pb) and (Ti, facilitated polarization rotations induced by the structural
Zr, Hf, Sn) with Bi and (Y, Fe, Sc, Ga, Al, In),229−242 and this instability.11,35,70,76 However, doping with Li+ is first used to
ABO3 can be used to modify the KNN materials. The KNN- improve the piezoelectric activity of KNN materi-
based materials are also modified by doping elements (e.g., V, als.101,166−173,394 Table 1 displays the piezoelectric activity of
Mn, Co, Ni, Cu, Zn, B, La, Ce, Pr, Nd, Dy, Yb, etc.) in the form Li+-doped KNN materials.101,162,166−173 There are a number of
of oxides, and electrical properties can be controlled by advantages of introducing Li+ into KNN materials. First, adding
tailoring the defect types. Recently, special ABO3 additives Li+ can increase TC, decrease TO−T, and slightly affect TR−O
containing Bi3+ and Zr4+ have been found to greatly promote values of KNN ceramics;174 thereby the O−T phase boundary
the piezoelectric activity of KNN-based materials by the can be formed, improving the piezoelectric activity of the
construction of R−T phase boundaries,106−113 where Bi3+ and material.101 Second, the doping with Li+ can also decrease the
Zr4+ can, respectively, lower TO−T and increase TR−O and Sb5+ sintering temperatures and improve the density of KNN
ions can further compact the O phase zone.106−113 By the materials.101,166−173 It was shown that d33 values of 188−324
thought of phase boundary, a large d33 of >400 pC/N was pC/N could be obtained by doping 6−8 mol % Li+ into KNN
attained in KNN-based ceramics by doping of Bi0.5M0.5ZrO3 ceramics due to the formed O−T phase boundary,101,166−173
(M = Na+ and/or Li+ and/or K+ and/or Ag+),106−113 and the and the actual Li+ content at maximum d33 also depends on the
different d33 values originate from the variance in TR−T.277 different processing methods.101,166−173 It is also worth noting
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Table 1. Piezoelectric Activity of Li+-Modified KNN is sensitive to not only the phase boundary and but also the
Materials with O−T Phase Boundaries compositions; thus, further investigation is necessary.
4.1.2. Li+ and Sb5+ Substitution. Many studies have
d33 (pC/ Tc
material system N) kp (°C) ref involved systematic investigation of the piezoelectric properties
of Li+- and Sb5+-codoped KNN materials, the general idea
K0.47Na0.47Li0.06NbO3 235 0.38 475 Guo101
being to shift TO−T to (or near to) room temperature by
(K,Na,Li)NbO3 324 0.54 Li and Wang166
modifying the Li+ and Sb5+ content.182−192 In fact, Li+ plays a
0.94K0.49Na0.51NbO3− 246 0.42 467 Li167
0.06LiNbO3 large part in the decreased TO−T of KNN,101,162,166−173,392−394
0.92Na0.535K0.48NbO3− 280 0.48 475 Li and Wang168 and Sb5+ can simultaneously decrease TO−T and increase
0.08LiNbO3 TR−O,106−110,251,392 as shown in Table 2. As a result, doping
0.93K0.5Na0.5NbO3− 274 Du169
0.07LiNbO3
Table 2. Effects of Li+, Sb5+, and Ta5+ on Both TO−T and
(K0.5Na0.5)0.935Li0.065NbO3 188 471 Wongsaenmai170
TR−O of a Pure KNN Ceramic101,251,254
(K0.5Na0.5)0.94Li0.06NbO3 235 0.42 Kakimoto171
0.94K0.5Na0.5NbO3− 215 0.41 450 Du172 1 mol % Li+ Sb5+ Ta5+
0.06LiNbO3
TO−T (°C) −30 −10.7 −4.0
0.93K0.5Na0.5NbO3− 240 0.35 Song173
0.07LiNbO3 TR−O (°C) +14.8 +2.3

with Li+ and Sb5+ can further move a material’s TO−T close to
that Guo et al. achieved the first breakthrough in d33 values of
room temperature. As shown in Table 3, codoping with Li+ and
Li+-modified KNN ceramics prepared by the conventional
solid-state method,101 and an enhanced d33 value of ∼235 pC/
N was reached when the TO−T was tuned to near room Table 3. Piezoelectric Activity of Li+- and Sb5+-Modified
temperature, which is one-third as much as a pure KNN KNN Ceramics with O−T Phase Boundaries
ceramic.101,166−174 However, such a d33 value is still inferior to d33 (pC/ Tc
those of most PZT ceramics,4,5 and thus, other attempts must material system N) kp (°C) ref
be made to further increase its d33 value.169,173,175−181 For 0.948(K0.5Na0.5)NbO3− 265 Zhang182
example, Song et al. increased the d33 values of 0.93KNN− 0.052LiSbO3
0.07LN ceramics from ∼195 to 240 pC/N by increasing their 0.95(K0.48Na0.52)NbO3−0.05LiSbO3 262 0.46 373 Wu183
grain sizes using two-step sintering methods (sintering at 1030 0.94(K0.5Na0.5)NbO3−0.06LiSbO3 212 0.46 358 Lin184
°C and subsequent annealing at 1050 °C).173 Du et al. studied 0.95K0.49Na0.51NbO3−0.05LiSbO3 256 0.43 340 Li185
the effects of both sintering temperatures and poling conditions 0.95(K0.40Na0.60)NbO3−0.05LiSbO3 280 0.49 364 Wu186
(e.g., poling temperature, poling electric field, etc.) on the 0.95(K0.42Na0.58)NbO3−0.05LiSbO3 270 0.47 364 Wu187
piezoelectric activity of KNN−LiNbO3 ceramics and found that (Na0.5K0.5)1−x(LiSb)xNb1−xO3 260 0.50 390 Zang188
two methods can further optimize their piezoelectric proper- 0.95K0.5Na0.5NbO3−0.05LiSLbO3 215 0.42 386 Palei189
ties.169,175,176 Zhao et al.177 reported that high piezoelectricity (Na0.474K0.474Li0.052)(Nb0.948Sb0.052) 242 0.42 Zhao190
O3
(d33 ≈ 314 pC/N) can be attained in Li+-modified KNN (Na0.5K0.5)0.945Li0.055Nb0.96Sb0.04O3 240 Li191
ceramics by adding excess Na+ (∼2.9%) and choosing optimum
sintering temperatures (∼1060 °C). Li and Wang et al.178
reported that a high converse piezoelectric coefficient (d33* ≈ Sb5+ can enhance the d33 values (∼210−280 pC/N) of KNN
538 pm/V) compared to PZT could be observed in Li+- materials.182−191 We can see from Table 3 that two different Li+
modified KNN ceramics when a low applied electric field (∼1 and Sb5+ doping methods were used to modify KNN, including
kV/mm) was used. In addition, they also developed a new LiSbO3182−190 and Li+/Sb5+.191 The O−T phase coexistence of
poling method to further improve the piezoelectricity by aging KNN−LiSbO 3 ceramics can be effected with LiSbO 3
and repoling-induced enhancement of the piezoelectricity (d33 compositions at 5−6%, leading to d33 values of 210−280 pC/
≈ 324 pC/N) in such a ceramic owing to both the defect N.182−190 For example, Zhang et al.182 reported that an
migration and the rotation of the spontaneous polarization.166 enhanced d33 value of ∼265 pC/N was observed in
This is considered the second major breakthrough with regard 0.948(K0.5Na0.5)NbO3−0.052LiSbO3 ceramics due to the
to the d33 values of Li-modified KNN ceramics. The Bridgman formation of O−T phase boundaries, showing the strong
method was used to prepare (001)-oriented 0.95KNN−0.05LN temperature dependence of d33. In the development of KNN-
single crystals, leading to a high d33 of 405 pC/N and a large based materials, Sb5+ plays a large part in the construction of
thickness electromechanical coupling factor (kt) of 61%,181 phase boundaries, especially for R−T.106−110 In addition, we
which can be regarded as the third breakthrough for this confirmed that adding Sb5+ can decrease the TR−O and TO−T
material system. It is well known that the TO−T in KNN has values of KNN materials to room temperature (see Figure
both advantages and disadvantages, i.e., a large d33 vs a poor 9),392 and thus, Sb5+ and other additives can result in a high
temperature stability.182 Higashide et al.,160 Hollenstein et piezoelectricity by forming R−T phase boundaries.106,107 As a
al.,161 and Zhai et al.245 investigated the temperature stability of result, Sb5+ plays a very important role in the construction of
the piezoelectric properties of Li+-modified KNN ceramics, and phase boundaries and the enhancement of piezoelectric activity
a poor temperature stability was demonstrated when the of KNN-based materials.
compositions were at the O−T phase boundary zone. However, 4.1.3. Li+ and Ta5+ Substitution. For KNN materials,
an opposite result has been found by Li and Wang et al., and adding both Li+ and Ta5+ has advantages similar to those of Li+
there is a slight variance in field-induced strain of Li+-doped and Sb5+,102,162,163,193−203 that is, the decreased TO−T near
KNN from room temperature to 175 °C.278 The authors room temperature can lead to a high piezoelectric activ-
wondered whether the temperature stability of KNN materials ity.102,162,163,193−203 However, we still find some differences
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ries,101,102,162,163,166−173,182−203,392−394 the d33 values of the


materials are usually less than 300 pC/N. As a result, a major
goal is the discovery of KNN-based materials with higher d33
values. Among the range of chemical modifications, codoping
with Li+, Ta5+, and Sb5+ can cause rapid decreases of TO−T in
KNN materials (see Table 5),12,156,157,204−214 and finally the
O−T phase boundary near room temperature can be more
rapidly tuned by controlling the elemental contents. For
example, Satio et al.12 reported that a high d33 value of ∼416
pC/N can be achieved in Li+, Ta5+, and Sb5+ codoped KNN
textured ceramics. Although such a high d33 can be comparable
to those of PZT materials,12 the expensive RTGG methods
used seriously limit their practical applications. If a similar
material system with a high d33 can be prepared by
conventional solid-state methods, the pace of their practical
Figure 9. Phase diagram and d33 values of (K0.48Na0.52)(Nb1−xSbx)O3 applications may be further accelerated. As a result, efforts have
ceramics.392 focused on developing KNN ceramic systems containing Li+,
Ta5+, and Sb5+ by conventional solid-state methods, and d33
values of >300 pC/N can often be attained by controlling the
between the two, namely, the addition of Li+ and Ta5+ more
ratios of three elements (e.g., Li+, Ta5+, and Sb5+).156,157,204−210
slowly decreases its TC value with respect to those modified by
As shown in Table 5, the composition-induced O−T phase
Li+ and Sb5+ (see Table 2).196,197,251,254 As a result, doping with
both Li+ and Ta5+ is another effective way to promote the boundary is largely responsible for the enhanced piezo-
piezoelectric activity of KNN materials without seriously electricity of KNN-based ceramics.12,156,157,204−214 For exam-
sacrificing its TC,196,197,254 as shown in Table 4. Guo et al.102 ple, excellent piezoelectric properties (d33 ≈ 413 pC/N) were
first reported that KNN−LiTaO3 ceramics possess the observed when low Li+ (∼2%) and high Ta5+ (∼18%) contents
enhanced piezoelectric properties of d33 ≈ 200 pC/N and kp were doped into KNN-based ceramics,204 and (K0.52Na0.45)-
≈ 0.36 when the compositions are located at the O−T phase (Nb0.88Sb0.09)O3−0.03LiTaO3 ceramics also exhibit a high d33
boundary. In addition, some references also show that a high value of ∼400 pC/N.205 However, these results show that their
Ta5+ content leads to a high d33 in KNN-based systems.193,195 d33 can be improved greatly by sacrificing the TC (≤230 °C)
For example, a d33 value of >250 pC/N was observed in KNN- values of KNN,204,205 as shown in Table 5. In addition, a high
based ceramics by doping a Ta content of ≥15%.193,195 Ta5+ content is still necessary to obtain a large d33 value in these
However, production costs inevitably increase when doping studies;157,204,207,211 otherwise, a lower d33 is often encoun-
excess Ta5+ into KNN materials, limiting their large-scale tered.212,214 As a result, codoping with Li+, Ta5+, and
industrial applications. As a result, it is necessary to develop Sb5+12,156,204−208 frequently contributes to the enhancement
methods to further promote the piezoelectricity of KNN of piezoelectric activity of KNN ceramics with respect to those
ceramics using a low Ta5+ content.196−198 For example, using doped by one or two of the three ele-
excess Li2O as a sintering aid and the formation of O−T phase ments, 101,102,162,163,166−173,182−203,392−394 but high costs
boundaries induces a high d33 of ∼250 pC/N in 0.95- (Ta5+) and low TC values may be two stubborn issues
(Na0.5K0.5)NbO3−0.05LiTaO3,198 and a high d33 value (∼268 impacting their practical application.
pC/N) in (K,Li)(Nb,Ta)O3 ceramics can also be attained by 4.1.5. Addition of ABO3. Perovskite ABO3 materials are
both constructing the same phase boundary and introducing often used to modify KNN in order to induce enhancement in
excess Na+.202 Although the piezoelectric activity of KNN piezoelectric activity by favoring the formation of phase
ceramics could be enhanced by adding Li+ and Ta5+, the boundaries,215−228 such as Bi0.5A0.5TiO3 (A = Na+,215,216
addition of Ta5+ should be avoided as far as possible or be used K + ,217 Li + 218 ), BTiO 3 (B = Ba 2+, 219 Sr2+ , 219 Ca 2+, 223
at low content levels with an eye toward practical applications. (Ba0.95Sr0.05)2+,224 [(Bi0.5Na0.5)0.94Ba0.06]2+,220 BiMO3 (M =
4.1.4. Li+, Sb5+, and Ta5+ Substitution. Although Li+, Li+ Sc3+,225 Al3+,226 Fe3+,227 Co3+ 228)), and others. Table 6 lists
and Ta5+ or Li+ and Sb5+ can improve the piezoelectric activity the piezoelectric properties of ABO3-modified KNN ce-
of KNN materials by forming O−T phase bounda- ramics.215−228 Doping with ABO3 can effectively promote the

Table 4. Piezoelectric Activity of Li+- and Ta5+-Modified KNN Ceramics with O−T Phase Boundaries

material system d33 (pC/N) kp Tc (°C) ref


0.93(K0.5Na0.5)NbO3−0.07LiTaO3 200 0.36 Guo102
(K0.5−x/2Na0.5−x/2Lix)(Nb1−y,Tay)O3 190 0.46 310 Hollenstein162
(Li0.04Na0.48K0.48)(Nb0.80Ta0.20)O3 215 0.43 Wang163
[(K0.458Na0.542)0.96Li0.04](Nb0.85Ta0.15)O3 298 0.52 366 Chang193
[(K0.5Na0.5)0.97Li0.03](Nb0.8Ta0.2)O3 234 0.51 358 Satio194
(K0.55Na0.45)0.965Li0.035Nb0.80Ta0.20O3 262 0.53 325 Zhang195
(Na0.535K0.485)0.926 Li0.074(Nb0.942Ta0.058)O3 276 0.46 ∼450 Shen196
[(Na0.535K0.480)0.942Li0.058](Nb0.94Ta0.06)O3 232 0.39 462 Zhao197
Li2O−0.95(Na0.5K0.5)NbO3−0.05LiTaO3 250 0.37 Kim198
(K0.5Na0.5)0.96Li0.04(Nb0.775Ta0.225)O3 208 0.48 320 Lin199

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Table 5. Piezoelectric Activity of Li-, Ta-, and Sb-Modified KNN Ceramics with O−T Phase Boundaries
material system d33 (pC/N) kp Tc (°C) ref
(K0.44Na0.52Li0.04)(Nb0.86Ta0.10Sb0.04)O3 416 0.61 253 Satio12
(K0.38Na0.58Li0.04)(Nb0.91,Ta0.05,Sb0.04)O3 306 0.48 Wu156
(K0.44Na0.52Li0.04)(Nb0.84Ta0.1Sb0.06)O3 345 ∼249 Akdogan157
(K0.45Na0.55)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3 413 0.50 ∼225 Gao204
(K0.52Na0.48−x)(Nb1−x−ySby)O3−xLiTaO3 400 0.54 ∼230 Zuo205
(Na0.52K0.44Li0.04)Nb0.87Sb0.08Ta0.05O3 376 0.44 ∼270 Du206
(Na0.5K0.5)0.975Li0.025Nb0.76Sb0.06Ta0.18O3 352 0.47 ∼210 Du207
(Na0.52K0.4375)(Nb0.9075 Sb0.05)O3−0.0425LiTaO3 321 0.52 315 Fu208
(Na0.52K0.48−xLix)Nb1−x−ySbxTayO3 308 0.51 339 Ming209
(K0.4425Na0.52Li0.0375)(Nb0.8925Sb0.07Ta0.0375)O3 304 0.48 271 Pang210
Li0.04(Na0.54K0.46)0.96Nb0.81Ta0.15Sb0.04O3 293 0.46 340 Noh211
Li0.02(Na0.55K0.45)0.98(Nb0.77Ta0.18Sb0.05)O3 256 0.42 Yoo212
0.96(K0.48Na0.52)(Nb0.95Ta0.05)O3−0.04LiSbO3 250 0.45 348 Wu214

Table 6. Piezoelectric Properties of ABO3-Modified KNN formation of O−T phase boundaries by decreasing a material’s
Ceramics T O−T values, inducing enhanced piezoelectricity.215−224
Although ABO3-type additives can increase the d33 values of
d33
(pC/ Tc KNN-based mateials,215−228 the resulting values are still inferior
material system N) kp (°C) ref to those of KNN ceramics containing Li+, Ta5+, and
0.97(K0.5Na0.5)NbO3− 195 0.43 375 Zuo215 Sb5+,156,157,204−211 as shown in Tables 5 and 6. However, the
0.03(Bi0.5Na0.5)TiO3 low cost of ABO3 may make it a potential candidate for
0.975(K0.5Na0.5)NbO3− 256 0.48 373 Du216 practical applications.
0.025(Bi0.5Na0.5)TiO3
4.1.6. Addition of ABO3 Multicomponents. KNN
0.98(K0.5Na0.5)NbO3−0.02(Bi0.5K0.5) 251 0.49 376 Du217
TiO3 ceramics doped with ABO3 multicomponents usually possess
0.98(K0.5Na0.5)NbO3− 172 0.37 381 Jiang218 enhanced piezoelectric behavior (d33 = 220−305 pC/N)
0.02Li0.5Bi0.5TiO3 together with high TC values of >300 °C,229−242 as shown in
0.94(Na0.5K0.5)NbO3−0.06BaTiO3 150 0.34 279 Wang219 Table 7. Results show that doping with most ABO 3
0.95(Na0.5K0.5)NbO3−0.05SrTiO3 195 0.37 289 Wang219 multicomponents can shift a material’s TO−T to room
0.96(Na0.5K0.5)NbO3− 256 0.43 395 Chen220 temperature, resulting in the formation of O−T phase
0.04(Bi0.5Na0.5)0.94Ba0.06TiO3 boundaries. As indicated in Table 7, the ABO3 materials
(K0.5Na0.5)NbO3−Ba(Zr0.05Ti0.95) 234 0.49 318 Lin221 containing Bi3+ are often used to modify KNN-based ceramics,
O3−MnO2
K0.5Na0.5NbO3− 203 0.45 342 Lin222
such as BiFeO3,229−232 BiScO3,233−235 BiAlO3,241 etc. Among
CaTi0.9Zr0.1O3+MnO2 BiMeO3 (Me = Fe, Sc, Al, etc.) additives, doping with BiFeO3
0.95(Na0.5K0.5)NbO3−0.05CaTiO3 241 0.41 306 Park223 or BiScO3 greatly favors increases in d33, and d33 values of >250
0.97(Na0.5K0.5)NbO3− 136 0.21 Kim224 pC/N are often obtained in such ternary systems by formation
0.03(Ba0.95Sr0.05)TiO3 of O−T phase boundaries.229−231,233 The differences in
0.9825K0.5Na0.5NbO3−0.0175BiScO3 253 0.48 351 Du226 increases in d33 mainly originate from the velocity of shifting
0.99(Na0.5K0.5)NbO3−0.01BiAlO3 202 0.46 372 Zuo225 TO−T. For example, Jiang et al.229 investigated KNN−LiSbO3−
0.99K0.5Na0.5NbO3− 144 0.34 370 Zhang227 BiFeO3 ternary systems in order to shift the TO−T nearer to
0.01Bi0.8La0.2FeO3
room temperature, finding that low amounts of BiFeO3 (0.4
(1−x)(Na0.5K0.5)NbO3−xBiCoO3 165 0.40 370 Xiao228
(x = 0.01) mol %) increase the d33 values from ∼202 to 260 pC/N. As a
result, BiFeO3 as an ABO3 component can effectively enhance

Table 7. Piezoelectric Properties of KNN Ceramics with ABO3 Multicomponents

material system d33 (pC/N) kp Tc (°C) ref


0.996(0.95Na0.5K0.5NbO3−0.05LiSbO3)−0.004BiFeO3 260 0.52 365 Jiang229
0.95(0.995Na0.5K0.5NbO3−0.005BiFeO3)−0.05LiSbO3 257 0.52 365 Jiang230
0.996[(K0.458Na0.542)0.96Li0.04](Nb0.85Ta0.15)O3−0.004BiFeO3 261 0.58 345 Chao231
0.995Li0.03(Na0.53K0.48)0.97Nb0.8Ta0.2O3−0.005BiFeO3 238 0.47 300 Zhou232
0.995(0.95K0.5Na0.5NbO3−0.05LiSbO3)−0.005BiScO3 280 0.49 ∼340 Li233
0.992(0.95K0.5Na0.5NbO3−0.05LiSbO3)−0.008BiScO3 305 0.54 315 Jiang234
0.99(Na0.485K0.485Li0.03)NbO3−0.01BiScO3 225 0.38 402 Sun235
0.998[0.95(K0.5Na0.5)NbO3−0.05LiSbO3]−0.002BiFe0.8Co0.2O3 276 0.48 340 Zhao236
0.96(0.99K0.5Na0.5NbO3−0.01Bi0.5Na0.5TiO3)−0.04LiSbO3 250 0.29 339 Liu237
0.938Na0.5K0.5NbO3−0.002BiNiO3−0.06LiSbO3 240 0.44 360 Liu238
(Li,K,Na)(Nb,Sb)O3−LiSbO3−(Ba,Ca)(Ti,Zr)O3 237 0.49 335 Wu239
K0.5Na0.5NbO3−LiNbO3−BNKT 240 0.46 469 Chen240
0.998(0.948 K0.5Na0.5NbO3−0.052LiSbO3)−0.002BiAlO3 233 0.35 349 Liu241
0.996(K0.475Na0.475Li0.05)(Nb0.95Sb0.05)O3−0.004Bi(Ni0.5Ti0.5)O3 253 0.52 ∼350 Yang242

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the piezoelectric activity of KNN−LiSbO3 ceramics by forming Table 8. Effect of K/Na Ratio on Piezoelectric Properties of
O−T phase boundaries at or near room temperature. However, KNN-Based Ceramics
doping with BiScO3 has different effects on the piezoelectric
d33 (pC/ Tc
activity of KNN-based ceramics.233,234 For example, a d33 value composition N) kP (°C) ref
of ∼305 pC/N was shown in K0.5Na0.5NbO3−LiSbO3−BiScO3
(KxNa0.96−xLi0.04)(Nb,Ta,Sb)O3 306 0.48 Wu156
ternary systems with pure tetragonal structures; the authors (x = 0.38)
reasoned that the phase boundary cannot play an important 0.95(KxNa1−x)NbO3−0.05LiSbO3 280 0.49 Wu186
role in the improved piezoelectric properties.234 However, we (x = 0.40)
found that the addition of BiScO3 results in increased TR−O (KxNa1−x)0.95Li0.05(Nb,Ta)O3 242 0.46 Wu244
values and decreased TO−T values of KNN;108,109 thus, the new (x = 0.42)
R−T phase boundary could be finally formed at room (KxNa1−x)0.94Li0.06NbO3 (x = 0.50) 220 0.43 Zhai245
temperature. In addition, the dielectric constant of this material (NaxKy)(Nb,Sb)−LiTaO3 183 0.33 Kang246
gradually increases with decreasing measurement temper- (KxNa0.96−xLi0.04)(Nb,Ta)O3 291 0.54 Chang247
(x = 0.44)
atures,234 suggesting the involvement of phase boundaries at
or near room temperature. As a result, further investigation into
this material system is necessary for understanding the origin of 4.1.8. Other Ions. As discussed before, chemical
its enhanced piezoelectricity.234 To further clarify this modifications (ion substitution (Li+, Ta5+, Sb5+), ABO3, etc.)
assumption, we characterized the dielectric constant of can improve the piezoelectric activity of KNN materials by
0.992(0.95K 0.5 Na 0.5 NbO 3 −0.05LiSbO 3 )−0.008BiScO 3 ce- constructing O−T phase boundaries. However, other elements
ramics at different temperatures, as shown in Figure 10. The may also affect the piezoelectricity of KNN materials,118,399−405
as shown in Table 9. We can observe from Table 9 that the
piezoelectric activity of KNN materials results from ion
substitutions of A and/or B.118,399−405 For example, doping
with Ag+ can enhance the d33 value of KNNST ceramics by
shifting TO−T to near room temperature.118,399 It was found
that the addition of Bi3+ and Zr4+ induces improvement in d33
of KNN by shifting a phase transition from pseudocubic to
orthorhombic phase.401 As a result, different ion substitution
can result in different piezoelectric activity of KNN materials
mainly due to the involvement of different phase bounda-
ries,118,399−405 and the enhancement in their piezoelectricity of
most ceramics is due to the O−T phase boundary.118,399,402
Figure 11a displays the d33 and TC values of ceramics with
different chemical modifications. It was found that the
piezoelectric activity is strongly dependent on the types of
the chemical modifications. In terms of the piezoelectric
activity, Li+-, Ta5+-, and Sb5+-modified KNN ceramics possess
Figure 10. εr−T curve of 0.992(0.95K0.5Na0.5NbO3−0.05LiSbO3)− larger d33 values with respect to others. As far as the TC value is
0.008BiScO3 ceramics. concerned, ceramics doped with Li+ or Li+−Ta5+ have higher
TC values than those doped with other additives. To further
understand the effects of doping elements on the piezo-
εr−T curve measured from −150 to 200 °C shows the
electricity, we give some samples and plot the d33 vs TO−T of
involvement of R−T phase boundaries in this material. This
KNN ceramics with different ion substitu-
suggests that enhanced d33 values of this material should be due
tions,101,102,156,169,182,184,188,193,195,204,214 as shown in Figure
to the R−T phase boundary and not a T phase.
11b. For the same doping elements, the d33 value is very
4.1.7. Ratio of K/Na. In 2007, our group observed a large
sensitive to the corresponding TO−T, and the d33 value can be
d33 of ∼306 pC/N in KNN-based ceramics by modifying K/Na
greatly increased for a TO−T near room temperature. More
ratios,156 and related research by other groups has further
interestingly, we found that a higher d33 value can only be
clarified this issue.245−247 In fact, the K/Na ratios of KNN
attained with Li+, Ta5+, and Sb5+ codoped KNN ceramics, even
materials were thought to modify PPT near room temper-
if a similar TO−T is involved.182,193,204 As a result, the
ature,156,186,244−247 helping to enhance their piezoelectric
piezoelectric activity of KNN-based materials is strongly
activity. Although the K/Na ratios strongly affect the
affected by not only the phase boundary but also the TO−T
piezoelectric activity of KNN-based ceramics, the optimum
value. In addition, some other factors also play a part in a
K/Na ratio is very sensitive to the actual compositions of the
material’s piezoelectric properties, such as poling conditions,169
KNN-based materials,156,186,244−247 as shown in Table 8. In the
microstructure,204 and electronegativity.204
references, the d33 values of KNN-based materials could be
improved by changing the K/Na ratio as their TO−T is 4.2. Rhombohedral−Orthorhombic Phase Boundaries
intrinsically shifted. 156,186,244−247 Zhai,245 Kang, 246 and It is well known that a pure KNN undergoes a series of
Chang247 et al. also promoted the piezoelectric activity of structural phase transitions as the measurement temperature
KNN-based ceramics by similar methods, but the K/Na ratio is increases (see Figure 13): TR−O(−123 °C) → TO−T(210 °C)
obviously different. As a result, the piezoelectric properties of → TC(410 °C).5,248,249 In section 4.1, much attention has been
KNN-based ceramics were enhanced mainly due to the paid to discussion of the O−T phase boundary of KNN
evolutions of phase structure induced by changing the K/Na materials, which has been an effective tool for enhancing their
ratio. piezoelectric activity over the past 10 years (refs 101, 102, 132,
2570 DOI: 10.1021/cr5006809
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Table 9. Piezoelectricity of KNN-Based Ceramics with Different Ion Substitutions


composition d33 (pC/N) kP Tc (°C) ref
(K0.42Na0.52Li0.04Ag0.02)(Nb0.91Ta0.05Sb0.04)O3 263 0.45 353 Wu118
0.98[(K0.4725Na0.4725Li0.055)0.98Ag0.02(Nb0.98Ta0.02)O3 237 0.39 470 Xiao399
(K0.5Na0.5)0.82Ag0.18NbO3 186 0.43 355 Lei400
(K0.50Na0.50)0.97Bi0.01(Nb0.98Zr0.02)O3 161 0.41 370 Wu401
(K0.5Na0.5)0.94Li0.06(W2/3Bi1/3)0.008Nb0.992O3 282 0.45 Du402
(K0.5Na0.5)0.92Li0.04Sr0.02Nb0.98Sb0.02O3 142 0.38 353 Hao403
(K0.5Na0.5)(Nb0.998Cu0.005)O3 112 0.38 440 Tan404
(K0.48Na0.48Ca0.02)(Nb0.85Ta0.15O3) 155 Coondoo405

Figure 11. (a) d33 vs TC of ceramics with different chemical modifications,12,97,101,102,104,106−118,166,277−285,392−405 and d33 vs TO−T values of the
ceramics.101,102,156,169,182,188,184,193,195,204,214

Figure 12. Phase diagrams of (a) (K0.5Na0.5)(Nb1−xTax)O3254 and (b) (1−y)K0.5Na0.5NbO3 −yBaZrO3397 ceramics.

Figure 13. Phase transitions of a pure KNN.

151−157, 159−168, 170−178, 182−197, 199−218, 220, 221, addition, it was found that doping with Ta5+ could decrease
224, and 229−247). However, the R−O phase boundary of both TC and TO−T and increase TR−O of KNN,254 similar to
KNN is often neglected, as such a phase transition is at low Sb5+.251,392 However, the TR−O value of Ta-doped KNN
temperatures (ca. −123 °C)248,249 and provides a poor d33.392 ceramic could not reach room temperature in the investigated
Recently, additives have been used to increase the TR−O values composition ranges (see Figure 12a),254 showing that the R−O
of KNN, including Sb5+,251,253,392 Ta5+,254 AZrO3 (A = Ba2+, phase boundary is difficult to induce by chemical modification.
Sr2+, Ca2+),397,398 BiScO3,252 etc.250,255,256,258−263 For example, Figure 12b plots the phase diagram of (1−x)K0.50Na0.50NbO3−
the TR−O value of (K0.48Na0.52)(Nb,Sb)O3 can be tuned to near xBaZrO3 solid solutions. For a pure KNN ceramic, the addition
room temperature by refining the Sb content (see Figure 9); of AZrO3 (A = Ba2+, Sr2+, or Ca2+) can shift its TR−O to room
thereby an improved d33 (∼230 pC/N) was demonstrated due temperature.397,398 Although the R−O phase boundary can be
to the coexistence of R−O ferroelectric mixed phases.251 In formed in KNN,250−252 the d33 value of ≤230 pC/N is usually
2571 DOI: 10.1021/cr5006809
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poorer with respect to those with O−T phase boundaries, as KNN, as collected from these references.250−254,397,398 The
shown in Table 10. Their d33 values are determined not only by addition of ions or ABO3 materials (e.g., Sb5+,251,392 Ta5+,254
BaZrO3,397 CaZrO3,398 SrZrO3,398 etc.) could simultaneously
Table 10. Piezoelectric Properties of KNN-Based Ceramics increase TR−O and decrease TO−T of KNN materials. As a result,
with TR−O it is reasonable that the R−T phase boundary should be formed
in KNN materials by controlling the composition ratios of the
d33
(pC/ TPPT Tc doped additives.
material system N) kp (°C) (°C) ref According to a number of references, we developed new
(Na0.52K0.48)(Nb1−ySby)O3 230 ∼Tr ∼190 Zuo251 methods to form new phase boundaries (e.g., R−T) in KNN
(y = 0.09) materials, as shown in Figure 14. Some additives were able to
(1−x)KNN−xCaZrO3 154 0.32 ∼Tr 320 Liang250
(x = 0.04)
(1−x)(Na0.5K0.5)NbO3− 210 0.45 ∼Tr 340 Zuo252
xBiScO3 (x = 0.02)

their R−O phase boundary but also by their chemical


modification types,250−252 and unfortunately the d33 is usually
increased by sacrificing TC.250−252 Although R−O KNN
materials possess a poor comprehensive performance of d33
and TC, it may help to design new phase boundaries (e.g., R−
T) by simultaneously moving TO−T and TR−O close to room
temperature.106−110 Detailed analysis is provided in section 4.3.
4.3. Rhombohedral−Tetragonal Phase Boundaries
As shown in sections 4.1 and 4.2, researchers have invested
much energy into the construction of two kinds of phase Figure 14. Diagram for constructing new phase boundaries in KNN
boundaries (i.e., O−T (refs 101, 102, 132, 151−157, 159−168, ceramics.
170−178, 182−197, 199−218, 220, 221, 224, and 229−247)
and R−O250−254,397,398) in KNN materials because of their
decrease TO−T of KNN to room temperature, including LiAO3
enhanced piezoelectric behavior, and a number of construction
(A = Nb 5+ , 101,172 Ta 5+ , 102,193,196 Sb 5+ 182,183,186,187 ),
methods were systematically addressed. More recently, several
Bi0.5B0.5TiO3 (B = Na+,215,216 K+,217 Li+ 218), CTiO3 (C =
attempts were made to shift the R−O boundary to near room
Ba2+,219 Sr2+,219 Ca2+ 223), etc.; their TR−O could be shifted to
temperature,250−254,397,398 and a low piezoelectric activity of d33
room temperature by the addition of DZrO3397,398 (D = Ba2+,
≤ 230 pC/N could be induced. In addition, it was proved that
Sr2+, Ca2+), BiEO3 (E = Sc3+,226,252 Al3+,225 Fe3+,227 Co3+ 228),
two kinds of phase boundaries (i.e., R−O and O−T) in KNN
Ta5+,254 Sb5+,251,253,257,392 etc. We were ultimately able to
belong to a polymorphic phase boundary (PPB), rather than a
induce the R−T phase boundary in KNN by doping different
typical morphotropic phase boundary (MPB).17,18,182,200,205
additives, and a series of KNN-based material systems with R−
The materials with PPBs possess a strong temperature
T phase boundaries has been developed.106−117,256,277,284,285 In
dependence of piezoelectric properties.17,18,182,200,205 At the
2013, our group first reported a high d33 value of ∼425 pC/N
same time, the d33 value of R−O or O−T KNN-based ceramics
in 0.96(K0.5Na0.5)0.95Li0.05Nb1−xSbxO3-0.04BaZrO3 ceramics by
is still poorer with respect to the lead-based ones. Faced with
constructing the R−T phase boundary (see Figure 15),256
such a bottleneck, we asked ourselves how to clarify these issues
matching previously reported results (∼416 pC/N) of textured
concerning KNN. Previously, it was reported that the R−T
KNN-based ceramics.12 In this paper, both Sb5+ and BaZrO3
phase boundary of PZT possesses a weak temperature
dependence of piezoelectric properties and a large d33;4,5
thus, we wanted to know whether a similar R−T phase
boundary could be induced for further improving both the
piezoelectric properties and the temperature stability of KNN
materials. By reviewing a number of the references, it seems
feasible to design a R−T phase boundary in KNN according to
the regulation of the formation of R−O and O−T phase
boundaries by doping in additives (refs 101, 102, 132,
151−157, 159−168, 170−178, 182−197, 199−218, 220, 221,
224, 229−247, and 250−254). Table 11 displays the influences
of different additives on the phase transition temperatures of

Table 11. Effect of Additives on the Phase Transition


Temperatures of KNN Ceramics

substitution (1 mol %) Ta5+ Sb5+ CaZrO3 BaZrO3 SrZrO3


TC (°C) −6.5 −25.1 −28.0 −28.0 −32.0
Figure 15. Phase diagram of KNLNSx−BZ ceramics. (Inset)
TO−T (°C) −4.0 −10.7 −11.0 −7.0 −13.0 Temperature dependence of εr and the composition dependence of
TR−O (°C) +2.3 +14.8 +17.0 +19.0 +19.0 d33.256

2572 DOI: 10.1021/cr5006809


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Table 12. Piezoelectric Properties of KNN-Based Ceramics with TR−T


material system d33 (pC/N) kp Tc (°C) ref
(Na0.52K0.40)(Nb0.84Sb0.08)O3−(0.08−x)LiTaO3−xBaZrO3 (x = 0.025) 365 0.45 ∼170 257
KNN−BaZrO3−LiSbO3 344 0.324 ∼176 258
(1−x)K0.5Na0.5Nb1−xSbxO3−xBi0.5Na0.5TiO3 380 0.35 ∼267 255
0.96(K0.5Na0.5)0.95Li0.05Nb1−xSbxO3−0.04BaZrO3 425 0.50 ∼197 256
(1−x)(K0.48Na0.52)(Nb0.95Sb0.05)O3−xBi0.5(Na0.7K0.2Li0.1)0.5ZrO3 380 0.46 290 260
(0.97−x)K0.48Na0.52NbO3−0.03Bi0.5(Na0.7K0.2Li0.1)0.5ZrO3−xB0.5Na0.5TiO3 285 0.40 347 261
0.992(K0.46Na0.54)0.965Li0.035Nb1−xSbxO3−0.008BiScO3 325 0.48 358 109

Figure 16. Relationship between phase boundary and d33 of (1−x)(K1−yNay)(Nb1−zSbz)O3−xBi0.5(Na1−wKw)0.5ZrO3 ceramics: (a) y = 0.48, z = 0.05,
w = 0.18; (b) x = 0.04, z = 0.05, w = 0.18; (c) x = 0.04, y = 0.48, w = 0.18; (d) x = 0.04, y = 0.48, z = 0.05.106

were used to simultaneously decrease the TO−T values and can be modified by forming different phase boundaries using
increase the TR−O values of KNN materials.251,397 However, we the optimization of the B and M elements in the
can observe from Table 12 that the ceramics often possess low materials.106−117,260,261,277,284,285 In addition, it is of great
TC values of <200 °C even if a large d33 (344−425 pC/N) was importance to note that the R−T phase boundary can be
observed.256−258 As a result, it is necessary to attain both a induced by using the additives mentioned above, leading to a
higher TC and a larger d33 in KNN when designing new phase large d33 of 400−490 pC/N.106−117,277,284,285 For example, a
boundaries.106−117 complicated system consisting of (1−x)(K1−yNay)(Nb1−zSbz)-
In the past, it was reported that doping with CZrO3 (C = O3−xBi0.5(Na1−wKw)0.5ZrO3 (0 ≤ x ≤ 0.05, 0.40 ≤ y ≤ 0.68, 0
Ba2+, Sr2+, Ca2+) can form three kinds of phase transition ≤ z ≤ 0.08, and 0 ≤ w ≤ 1) ceramics was developed and
temperatures (i.e., TC, TR−O, and TO−T) in KNN.397,398 In prepared via the conventional solid-state method,106 and the
addition, the effects of CZrO3 on their TC, TR−O, and TO−T are R−T phase boundary was constructed by refining the x, y, z,
almost independent of the types of A site (e.g., Ba2+, Sr2+, and w values of such a material system,106 i.e., 0.035 < x <
Ca2+), and therefore, Zr4+ plays an important role in the phase 0.045, 0.44 ≤ y ≤ 0.64, 0.02 < z ≤ 0.05, and 0 ≤ w ≤ 1 (see
transition temperatures (especially TR−O).397,398 Previously, it Figure 16). By forming the R−T phase boundary, a good
was reported that adding Bi3+ can shift the TO−T of KNN comprehensive performance of d33 and TC (e.g., d33 ≈ 390−490
materials.119,401 As a result, Bi3+ and Zr4+ could be used to tune pC/N and TC ≈ 217−304 °C) was also shown.106 More
the TR−O and TO−T of KNN, forming the R−T phase boundary importantly, we further studied the role of M in (Bi0.5M0.5ZrO3)
by simultaneously shifting TR−O and TO−T using additives in the piezoelectric properties of 0.96(K 0.48 Na 0.52 )-
containing two such elements. To maintain valence balance, we (Nb0.95Sb0.05)O3−0.04(Bi0.5M0.5)ZrO3 ceramics.277 The d33
constructed the new material Bi0.5M0.5ZrO3 (M = Na, Li, K, Ag, was found to be strongly dependent on the nature of M
(Na, Li), (Na, K), (Na, Ag), (K, Li), (Ag, Li), (Ag, Li), (Ag, K), because of the change of the R−T phase transition temperature
(Na, K, Li), (Na, K, Ag), (Na, Li, K), etc.),277 which was used (TR−T), and the ceramics have high d33 values of 450−490 pC/
to modify the KNN-based materials (see Figure 14). As a result, N, apart from those doped with Li+.277 As a result, we were able
we developed new KNN-based material systems consisting of to realize a larger breakthrough in the piezoelectric activity of
(1−x)(K,Na)(Nb,B)O3−xBi0.5M0.5ZrO3,106−117,277 where B = KNN by forming R−T phase boundaries, and the TR−T leads to
none, Sb5+, and Ta5+; M = Na, Li, K, Ag, (Na, Li), (Na, K), different d33 values. In addition, a series of KNN binary or
(Na, Ag), (K, Li), (Ag, Li), (Ag, Li), (Ag, K), (Na, K, Li), (Na, ternary systems with R−T phase boundaries was prepared
K, Ag), (Na, Li, K), etc.277 The piezoelectric properties of KNN according to our objective of realizing both high TC and d33
2573 DOI: 10.1021/cr5006809
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values. 106−117,260,261,396 For example, lead-free (1−x)- the way for practical applications to be “Lead-free at last”. We
(K0.48Na0.52)(Nb0.95Sb0.05)O3−xBi0.5(Na0.7K0.2Li0.1)0.5ZrO3 ce- believe that such material systems with R−T phase boundaries
ramics show a high d33 of ∼380 pC/N as well as a high TC are very promising candidates for potassium−sodium niobate
of ∼290 °C (see Figure 17);260 a high d33 of ∼285 pC/N and a piezoceramics.
4.4. Dopant Engineering
It is well known that the piezoelectric properties of KNN can
be greatly promoted by constructing phase boundaries using
different additives, that is, the formation of phase boundaries
driven by additives plays a large part in their improved
piezoelectric properties. However, other factors may affect the
electrical properties of KNN-based materials. In this section, we
will briefly review the dopant engineering in KNN-based
materials.
4.4.1. Doping with Equipollent Metals. Equipollent
metals are usually used to substitute the A or B site of KNN,
where Li+ often substitutes the A site101,166−173 and Sb5+ (refs
182−192, 251, and 392) and/or Ta5+ (refs 102, 162, 163,
193−203, and 254) are often used to replace the B
site.12,156,157,204−214 The main objective of these additives is
Figure 17. Phase diagram of (1−x)KNNS−xBNKLZ ceramics. (Inset) to induce the formation of phase boundaries by shifting phase
Thermal stability of the d33 value.260 transition temperatures (T R − O , T O− T , and T C ) of
KNN.101,102,156,157,162,163,166−203,251,254 For example, the Li+
high TC of ∼347 °C was also found in the ternary system can decrease the TO−T as well as increase both TR−O and TC
consisting of (0.97−x)K0.48Na0.52NbO3− of KNN,101,166−173 and doping with Sb5+ or Ta5+ can decrease
0.03Bi0.5(Na0.7K0.2Li0.1)0.5ZrO3−xB0.5Na0.5TiO3 with an R−T both TO−T and TC as well as increase TR−O of KNN (see Figure
phase boundary.261 In addition, good comprehensive perform- 9 and 12a).251,254 The Li, Ta, or Sb can cause the shift of three
ance of d33 and TC was also observed in other KNN material kinds of phase transition temperatures (TR−O, TO−T, and TC) of
systems (see Figures 16−18).106,109,260 As a result, the KNN materials (refs 101, 102, 156, 157, 162, 163, 166−203,
251, and 254), and thus, the enhanced piezoelectric properties
of Li+-, Ta5+-, or Sb5+-modified KNN materials originate from
the formation of different phase boundaries. As a result,
different phase boundaries can be effected by introducing one
or more elements to KNN, the main advantage of these
elements being to simultaneously shift its TR−O, TO−T, and TC.
Other factors may also be responsible for the enhanced
piezoelectric activity of KNN. For example, Li, Ta, and Sb have
the same valence as the A or B sites of KNN, which can avoid
the generation of certain defects. Recently, Safari et al.267
proposed that sp3 hybridization of the covalent over the ionic
bond should result in enhanced d33 values of (Li, Ta, Sb)
codoped KNN ceramics because the higher electronegativities
of Ta5+ and Sb5+ can increase the covalence of the bonds with
respect to Nb5+. Zhang et al.204 also proposed that the high
electronegativity of Sb5+ is responsible for the enhanced
Figure 18. Phase diagram of the KNLNSx−BS ceramics. (Inset) piezoelectric properties of KNN-based ceramics. As a result,
Composition dependence of the d33 values.109 some factors (electron configuration, ligand field theory,
covalence, etc.) are also considered for improving the electrical
piezoelectric activity of KNN could be dramatically enhanced properties by doping additives.
by forming R−T phase boundaries using the refinement of 4.4.2. Doping with Aliovalent Metals. 4.4.2.1. Aliovalent
material systems,106−112,256,260,261,277,284,285,396 and both a large Metals at the Nb Site. Aliovalent metals are often used to tailor
d33 and a high TC could be realized by optimizing their the electrical properties of KNN materials by forming point
compositions.106−117,277,284,285,396 defects.128,145,267,279−281,406−415 It is usually accepted that the
As far as KNN-based materials are concerned, we compared defect dipoles formed by acceptor dopants for charge balance
our results with previously reported ones (see Figure 19). One will prohibit domain−wall motion and then result in “harden-
can see from Figure 19a that the R−T phase boundary is a ing” of KNN. In the past, Cu-modified KNN systems have been
more useful way to promote the piezoelectric activity of KNN- extensively studied because of their high mechanical quality
based ceramics with respect to others (e.g., O−T and R−O). In factor;267 such a high Qm is due to the “hardening” effect. For
addition, the comprehensive performance of d33 and TC in example, Hoffmann et al. proposed that the “hardening”
KNN is superior to those of BT- and BNT-based materials (see behavior of Cu-doped KNN ceramics originates from the
Figure 19b). As a result, the R−T phase boundary can greatly impediment of domain−wall motion induced by two kinds of
promote the piezoelectric activity of KNN-based ce- defect complexes with oxygen vacancies ((CuNb ‴ − V••O )′ and
•• •• • 267,411,414
ramics,106−117,260,261,277,284,285,396 and our finding may pave (VO − CuNb ‴ − VO ) ). For Mn-modified KNN single
2574 DOI: 10.1021/cr5006809
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Figure 19. Room-temperature d33 as a function of TC for (a) KNN-based ceramics and our work90−265,277,284,285,392−405 and (b) BNT, BT-based
ceramics, and our work.16,17,35−90

crystals, the conductivity can be more quickly decreased after VK → V′K + h+ (6)
annealing under the same conditions because the Mn2+ valence
gradually becomes higher by absorbing electron holes.128 As a result, the vacancy and electron will be easily recombined
Similarly, it was also found that Mn2+ can absorb the free and eliminated during processing, which results in increasing
carrier holes from the volatilization of alkaline ions in Mn2+- resistivity. In addition, the “softening” characteristics also
doped KNN thin films, inducing enhanced ferroelectric promote their piezoelectric properties.148 It was reported that
properties.408,409,412 Yao et al. reported that titanium diffusions Dy3+ substitutions at the A site in KNN can be expressed by eq
strongly affected the composition, structure, and dielectric 7.417
properties of Ti4+-doped KNN thin films because both holes K 0.5Na 0.5NbO3
and oxygen vacancies will be generated, as shown in eqs 2 and Dy2O3 ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ 2Dy ••
Na
+ 4V′Na + 3OO (7)
3.407
For maintaining charge neutrality, electrons will be generated
Nb
Ti ↔ Ti′Nb + h• (2) due to Dy3+ as a donor and a Na vacancy was also observed.
The net dipole moment of two defects may be formed,
Nb2O5 inducing the maximum dielectric constant of Dy2O3-doped
2TiO2 ←⎯⎯⎯→ 2Ti′Nb + 4OO + V ••
O + 2e′ (3) KNN ceramics.417
High piezoelectricity of KNN-based materials mainly
Recently, the influences of elements with a higher valence on originates from the formation of phase boundaries driven by
the properties of KNN materials have been studied, and it was different additives, but other factors should not be neglected,
found that the concentration of oxygen vacancies is restrained such as ion types (e.g., electron configuration, ligand field
because W6+ can replace the Nb site of KNN (see eq 4).415 The theory, covalence, etc.), defect types, and their relation with
dielectric properties can be modified well by controlling the electrical properties, and so on. Understanding dopant
type of defect and the concentration of oxygen vacancies. engineering will benefit the development of physical mecha-
2WO3 + V •• •• nisms for enhanced electrical properties.
O = 2W Nb + 6O (4)
4.5. Supplementary Tools
As a result, the electrical properties of KNN can be modified by
As mentioned above, many attempts have been made to
tailoring the different defect types induced using aliovalent
promote the piezoelectric activity of KNN-based materials by
metals.
inducing three kinds of phase boundaries [e.g., O−T (refs 101,
4.4.2.2. Aliovalent Metals at the (Na, K) Site. In the past,
102, 132, 151−157, 159−168, 170−178, 182−197, 199−218,
substitution of some aliovalent ions (Ba2+,137,148 Pb2+,416
220, 221, 224, and 229−247), R−O,251,254,392,397,398 and R−
Dy3+ 417) at the A site can promote the piezoelectric properties
T106−117,256,260,261,277,284,285,396], including ion substitutions
of KNN materials because of different defect structure and
(Li+, Ta5+, Sb5+, etc.), the formation of solid solutions, K/Na
improved microstructure.416−419 Importantly, we illuminated
ratio, and others. In addition, other methods besides the
the effects of different defect types on the electrical properties
construction of phase boundaries also affect the piezoelectricity
of KNN-based materials by introducing aliovalent elements to
of KNN-based materials, such as sintering temper-
the A site. For example, an extra electron (e−) can be easily
atures,165,420−432 reactive template grain growth,12,203,433−446
generated for keeping valence balance when Ba2+ is used to
spark-plasma sintering, 1 2 7 , 4 4 7 − 4 5 2 non sto ichiom e-
replace the A site of KNN-based materials (see eq 5).148
try,113,166,168,453−467 two-step sintering,245,480−483 single crys-
Ba′K → BaK + e− (5) tal,120,484−508,547−551 poling conditions,166,169,265,520−522 sinter-
ing aids and sintering atmosphere,130,140,143,147,498,523−546 thin
At the same time, the K+ vacancy is formed due to the films,553−590 and extrinsic factors (density,3,121,127,135,249 grain
evaporation of K+ during processing and preparation,419 as size,124,132,271,537,539,610−613 domain struc-
shown in eq 6. ture,446,268,269,406,614−622 etc.). In this section, we briefly
2575 DOI: 10.1021/cr5006809
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Table 13. Effect of Sintering Temperatures on the Piezoelectric Activity of KNN-Based Ceramics
compositions Tsintering (°C) d33 (pC/N) kP Tc (°C) ref
0.96K0.46Na0.54Nb0.95Sb0.05O3−0.04Bi0.5(Na0.82K0.18)0.5ZrO3 1075 465 0.43 233 Wu112
[(Na0.535K0.480)0.966Li0.058](Nb0.90Ta0.10)O3 1090 268 0.46 445 Zhao165
0.058LiNbO3−0.942(Na0.535K0.480)NbO3 1060 314 0.41 490 Zhao177
(Na0.535K0.485)0.926Li0.074(Nb0.942Ta0.058)O3 1000 276 0.46 ∼450 Li421
0.92(Na0.535K0.48)NbO3−0.08LiNbO3 950 280 0.483 Li and Wang422

Table 14. Piezoelectric Properties of KNN-Based Ceramics Prepared by the RTGG Method
composition orientation d33 (pC/N) kP Tc (°C) ref
(K0.44Na0.52Li0.04)(Nb0.86Ta0.10Sb0.04)O3 ⟨001⟩ 416 0.61 253 Satio12
(Na0.50K0.47Li0.03)(Nb0.8Ta0.2)O3 + MnO2 + Li2CO3 ⟨h00⟩ 310 0.46 ∼320 Cho203
(K0.5Na0.5)(Nb0.97Sb0.03)O3 ⟨001⟩ 208 0.64 352 Chang433
(K0.463Na0.537)0.946Li0.054NbO3 ⟨001⟩ 254 0.43 450 Hao434

Table 15. Piezoelectric Properties of KNN-Based Ceramics Prepared by Other Nonconventional Techniques
composition preparation technique Tsintering (°C) d33 (pC/N) kP Tc (°C) ref.
(Na0.52K0.44Li0.04)(Nb0.86Ta0.06Sb0.08)O3 SPS + sol−gel 296 0.50 Wang448
(Li0.04K0.44Na0.52)(Nb0.85Ta0.15)O3 SPS 900 225 0.44 Li450
(Na0.535K0.485)0.95Li0.05(Nb0.8Ta0.2)O3 SPS 900 243 0.46 450 Li451

introduce the influences of these methods on the electrical compensate for their losses during processing at a temper-
properties and the corresponding physical mechanism. ature.112,165,177,421−431
4.5.1. Sintering Temperature. The sintering temperature 4.5.2. Reactive Template Grain Growth Method.
is usually thought to strongly affect the piezoelectric activity of Excellent piezoelectric parameters (dijk, gikk, kij, etc.) are
KNN-based materials because of the involvement of oxygen required for some piezoelectric devices.468,469 The reactive
vacancies induced by the loss of K+ and Na+ during the template grain growth (RTGG) method could effectively
sintering process.112,165,177,421−431,470 However, it is difficult to improve the piezoelectric coefficients of a material due to more
maintain the stoichiometric compositions of KNN materials efficient alignment of the polar vectors, resulting in the increase
due to this facile loss of K+ and Na+. of poling efficiency.12,203,433,434,468,469 For KNN material
Recently, sintering with compensation of the alkali metal loss systems, the initial breakthrough was the realization of a large
has been conducted to solve this issue, whereby enhanced d33 d33 value (∼416 pC/N) in (K0.44Na0.52Li0.04)-
values of 268−314 pC/N could be obtained,112,165,419−431 as (Nb0.86Ta0.10Sb0.04)O3 ceramics prepared by the RTGG
shown in Table 13. For example, Zhang et al.165 prepared method.12 In this work, the d33 value was found to match
LiTaO3-doped (K,Na)NbO3 ceramics using both optimum those of most PZT ceramics, spurring further interest in
sintering temperatures and excess Na+ with the aim of improving the piezoelectricity of KNN-based ceramics by the
controlling Na+ loss, and a high d33 value of ∼268 pC/N was RTGG method.12,203,433,434,468,469 For example, ⟨001⟩-oriented
induced, which is much larger than those doped with LiTaO3 (K0.5Na0.5)(Nb0.97Sb0.03)O3 ceramics were prepared by the
prepared by the conventional methods.102,198 In addition, they RTGG methods using NaNbO3 templates;433 these materials
possessed enhanced piezoelectric properties of kp = 0.64, k31 =
investigated the electrical properties of 0.942(Na0.535K0.480)-
0.37, d33 = 208−218 pC/N, and d31 = −82 pC/N. Although
NbO3−0.058LiNbO3 by emphasizing the influence of sintering
textured KNN-based ceramics have better piezoelectric proper-
temperatures as well as excess Na+,177 and an enhanced
ties with respect to nontextured ones owing to the easier
piezoelectric coefficient of ∼314 pC/N was also attained when
rotation of the polarization axis during the poling process (see
the material was sintered at 1060 °C. Li et al.421,422 also Table 14),12,203,433,434,468,469 they are not suitable for practical
investigated the influences of the sintering temperature on the applications due to high costs and their complicated
phase structure, microstructure, and electrical properties of preparation process.
(Na 0.5 35 K 0 .48 5 ) 0.9 26 Li 0 .07 4 (Nb 0.9 42 Ta 0. 058 )O 3 and 0.92- 4.5.3. Spark-Plasma Sintering. Special sintering techni-
(Na0.535K0.48)NbO3−0.08LiNbO3 ceramics, showing that the ques including hot pressing and spark-plasma sintering (SPS)
optimized sintering temperature is a critical factor to determine have been used in order to overcome the difficulties
their d33. More recently, we realized a large d33 (∼465 pC/N) encountered in fabricating high-density KNN materials. SPS
in 0.96K0.46Na0.54Nb0.95Sb0.05O3−0.04Bi0.5(Na0.82K0.18)0.5ZrO3 has a number of advantages, such as a rapid heating rate and
ceramics by optimizing the sintering temperatures, where the short soaking time.127,447−452 Related research has shown that
TR−T values and alkali metal content could be tailored by the SPS method can effectively promote the piezoelectric
changing their sintering temperatures.112 As discussed above, activity of KNN by inducing improved microstruc-
the main objective of this research is to suppress K+ and Na+ ture,127,447−452 as shown in Table 15. Li et al.127,447,450,451
loss by optimizing the sintering temperatures as well as extensively studied the microstructure and electrical properties
compensating for the volatile elements according to the of KNN-based ceramics prepared by SPS methods. For
nominal nonstoichiometric formulas,112,165,177,421−431 in which example, in 2006, the SPS was explored to solve the poor
the sum of molar fractions of atoms substituting the A site in densification of a pure KNN ceramic,127 and a d33 value of 148
ABO3 is above 1 mol, so that the superfluous parts can pC/N was obtained in highly dense KNN ceramics (theoretical
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Table 16. Piezoelectric Properties of Nonstoichiometric KNN-Based Ceramics


compositions d33 (pC/N) kP Tsintering (°C) ref
0.96(K0.46Na0.54+x)Nb0.95Sb0.05O3−0.04Bi0.5(Na0.82K0.18)0.5ZrO3 496 0.47 1075 Wu113
(1−x)(Na0.535K0.48)NbO3−xLiNbO3 (x = 0.08) 324a 950 Li and Wang166
(1−x)(Na0.535K0.48)NbO3−xLiNbO3 (x = 0.08) 280 0.483 950 Li and Wang168
(K0.48Na0.48Li0.04)1+x(Nb0.90Sb0.06Ta0.04)O3 (x = 0.01) 310 0.6 1090 Lin461
[(Na0.535K0.48)0.942Li0.058](Nb1−xSbx)O3 (x = 0.06) 298 0.345 1040 Zhang462
[(Na0.535K0.480)0.942Li0.058](Nb0.86Ta0.10Sb0.04)O3 264 0.356 1090 Zhang463
a
Repoling treatment.

density > 99%) at a low processing temperature of ∼920 °C. In ing their piezoelectric activity by changing the stabilization of
addition, they also prepared a high-density KNN piezoceramic the crystalline symmetries. More importantly, nonstoichiomet-
by the combination of a facile hydrothermal route and SPS,447 ric KNN-based ceramics possess much larger d33 values than
the d33 of which was shown to reach ∼135 pC/N, which is stoichiometric ones with the same composition, as shown in
almost twice as much as those of samples using powders Tables 16 and 17.101,184,212 In 2014, we attained a high
prepared from the solid-state reaction. More recently, Wang et
al. 448 reported that highly dense (Na 0.52 K 0.44 Li 0.04 )- Table 17. Piezoelectric Properties of Stoichiometric KNN-
(Nb0.86Ta0.06Sb0.08)O3 nanoceramics can be fabricated by SPS Based Ceramics
methods using nanopowders (11−34 nm), and a piezo-
d33
electricity of d33 ≈ 296 pC/N was observed, showing that the compositions (pC/N) kP ref
combination of nanopowders and SPS techniques are an (1−x)(Na0.50K0.50)NbO3−xLiNbO3 (x = 0.08) 164 0.35 Guo101
effective way to prepare fine-grained potassium−sodium 0.94(K0.5Na0.5)NbO3−0.06LiSbO3 212 0.46 Lin184
niobate ceramics with excellent elelctrical properties. These Li0.02(Na0.55K0.45)0.98(Nb0.77Ta0.18Sb0.05)O3 256 0.42 Yoo212
results show that an enhanced piezoelectric activity of the SPS- 0.96(K0.46Na0.54+x)Nb0.95Sb0.05O3 436 0.44 Wu113
sintered samples could be attributed to the lower sintering −0.04Bi0.5(Na0.82K0.18)0.5ZrO3
temperatures and the higher densities, which is superior to
those sintered by the conventional pressureless technique.449 In piezoelectric activity (e.g., d33 ≈ 496 pC/N and kp ≈ 47%) in
addition, related investigations were able to more clearly clarify 0.96(K0.46Na0.54+x)Nb0.95Sb0.05O3−0.04Bi0.5(Na0.82K0.18)0.5ZrO3
the relationships between microstructure and electrical proper- ceramics by doping nonstoichiometric sodium,113 and a
ties of KNN-based materials.127,447−452 As far as practical rhombohedral−tetragonal phase boundary was constructed in
applications are concerned, SPS is not as widely applied in ceramics with a wide Na+ nonstoichiometry.113 A higher d33
industry as the RTGG method is. value was observed in ceramics with an excess of 0.5% Na+ with
4.5.4. Nonstoichiometry. The composition fluctuations respect to those with stoichiometric ratios.113 Thus, the
seriously affect the electrical properties of KNN-based materials addition of nonstoichiometric alkali metals makes a large
due to alkali metal evaporation, which is a serious issue despite contribution to promoting the piezoelectric activity of KNN-
the significant breakthroughs in its synthesis and character- based ceramics.
ization.453 The deviation from stoichiometry during the Previously, it was shown that nonstoichiometric KNN-based
synthesis is a result of the strongly hygroscopic nature of ceramics with A/B < 1 possess an improved piezoelectricity due
alkaline carbonates, especially potassium carbonate.454 As a to the microstructure evolutions induced by the formation of a
result, controlling the alkali metal loss in KNN during its ferroelectric secondary phase.132,135,457,465 For example, Rubio-
processing and sintering is a critical issue.453,455 Marcos et al.132 systematically studied the effects of A/B (A =
It is well known that dense KNN ceramics must endure a (K0.44Na0.52Li0.04), B = (Nb0.86Ta0.10Sb0.04), A/B = 0.94) on the
high processing temperature of ∼1100 °C, whereby chemical phase structure and electrical properties of (K0.44Na0.52Li0.04)-
composition fluctuations cannot be avoided due to the (Nb0.86Ta0.10Sb0.04)O3 ceramics, and the electrical properties of
evaporation of some elements.113,453−456 In addition, chemical nonstoichiometric compositions were found to improve due to
composition deviation may be also caused during weighing due good homogeneity induced by the grain growth as well as the
to the deliquescence of Na2CO3/K2CO3. As a result, the loss of presence of a secondary ferroelectric tungsten−bronze phase
alkali metals negatively affects the electrical properties of KNN (e.g., K3LiNb6O17). As a result, the effects of nonstoichiome-
materials, and much attention has been focused on how to tricity and stoichiometricity on the microstructure and electrical
maintain the stoichiometric ratios of KNN.166,168,456−467 Table properties of KNN-based materials require further clarification,
16 shows the d33 values of published nonstoichiometric KNN- and further physical analysis should be conducted.
based ceramics.113,166,168,461−463 Excess alkali metals were used 4.5.5. Two-Step Sintering. The normal sintering
to suppress the chemical composition fluctuations of KNN- technique is to heat the green compact at a given rate; then
based ceramics,113,166,168,461−467 and enhanced piezoelectric the sample is kept at a higher temperature in order to reach the
properties were observed (see Table 16). These results show maximum density. However, it is difficult to achieve a material
that the calcining and sintering temperatures of KNN have with high density, homogeneous microstructure, and small
been strongly affected by the nonstoichiometric con- grain size by normal sintering. In 2000, a two-stage sintering
tent.282,283,456 The sintering temperatures of KNN were (TSS) technique developed by Chen et al. was shown to
decreased when the A site was excessive168 and then raised resolve this issue.546 In the TSS method, the full densification
when the B site was excessive.457 For example, Rubio-Marcos et without grain growth after the second-step temperature can be
al.283 reported that excess K+ may induce a displacement of Li+ achieved by the competition between the driving forces of grain
from (K0.44+xNa0.52Li0.04)(Nb0.86Ta0.10Sb0.04)O3, seriously affect- boundary-controlled densification and grain boundary-con-
2577 DOI: 10.1021/cr5006809
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trolled grain growth.114,245,471−483,546 First, the green samples heated to a high temperature (T1) in order to obtain a
are heated to a certain temperature for guaranteeing a uniform relatively high density and then are rapidly cooled and held at a
pore microstructure (relative densities > 75%) and minimizing low temperature (T2). Usually, the piezoelectricity of KNN-
grain growth; they are then cooled and held at a lower based ceramics is very sensitive to the sintering temper-
temperature for a long dwell time, where a low sintering atures,112,165,177,421−431,470 that is, enhanced piezoelectric
temperature results in decreased grain growths, and a long activity can be only attained in a narrow sintering temperature.
dwell time provides enough energy for improving its density.546 However, the TSS method is suitable for preparing KNN-based
Slower kinetics are involved when second-step sintering ceramics because the ceramics can be densitified by eradicating
proceeds in a frozen microstructure, but it is enough to achieve the pores due to the decreased loss of the alkali metals with a
full density and suppress grain growth.114,245,471−483,546 low melting point.114,245,480−483 For example, a pure KNN
To suppress or eliminate grain growth of electroceramics ceramic was prepared by the TSS method,482 and the resulting
during sintering, the TSS technique has attracted much dense microstructure led to its enhanced piezoelectricity. In
attention because it is possible to decrease the grain size and addition, the sintering temperature (T2) range can be widened
improve the density of sintered samples. For solving the narrow significantly for pure or chemically modified KNN ceramics
processing window of a ceramic, the TSS technique has also using TSS,245,480−483 after which their electrical properties were
been used to widern the sintering temperatures of lead-based mostly improved or maintained. The 0.9625Na0.5K0.5NbO3−
and lead-free piezoceramics, 114,245,471−483,546 such as 0.0375LiTa0.4Sb0.6O3 ceramics possess good electrical proper-
BaTiO3,471−475 Bi0.5Na0.5TiO3,476−478 BiScO3−PbTiO3,479 and ties together with a wide sintering temperature range (T2 =
K0.5Na0.5NbO3.114,245,480−483 The processing procedure for this 1000−1075 °C) when the TSS technique was used,483 and the
method is summarized in Figure 20: The samples are first TSS method also widens the sintering temperature range
(1090−1130 °C) of (KxNa1−x)0.94Li0.06NbO3 ceramics and
improves its piezoelectric activity.245 Recently, we also realized
a high d33 (348−416 pC/N) and wide sintering temperatures
(800−1130 °C) in 0.955(K0.42Na0.58)(Nb0.96Sb0.04)O3−0.045-
(Bi0.5K0.5)0.90Zn0.10ZrO3 ceramics using the TSS technique.114
As a result, the TSS technique can improve the density and
widen the sintering temperatures of KNN-based material
systems, resulting in an enhanced d33 value.
4.5.6. Single Crystals. The ferroelectric domains of
polycrystalline piezoceramics cannot be aligned completely
along one direction during poling owing to their randomly
oriented grains, easily resulting in degraded electrical proper-
ties. However, the domains of single crystals can be more easily
rotated during the poling fields.120,484−508,549−551 As a result,
single crystals may become an effective way to improve the
piezoelectric activity of alkali niobate materials by controlling
their domain engineering and crystal orientations (refs
484−493, 498, 504−509, and 547−551). Several methods
have been used to prepare KNN-based single crystals, such as
solid-state crystal growth,485,498,505,507,508 the flux meth-
Figure 20. Program schedule of conventional sintering and two-step od,486,487,490,491,493 the Bridgman method,181 top-seeded
sintering. solution growth,488,489,504 and the floating zone method.492
Table 18 shows the piezoelectric properties of KNN-based
single crystals grown by different methods. Among reported
results, one of the most exciting is that 0.95KNN−0.05LiNbO3

Table 18. Electrical Properties of KNN-Based Single Crystals Grown by Different Methods

compositions preparation method Pr (μC/cm2) εr K33 d33 (pC/N) ref


K0.53Na0.47NbO3 flux method 600 110 Kizaki484
K0.5Na0.5NbO3 solid-state crystal growth 17 1015 80 Uršič485
K0.5Na0.5NbO3 flux method 18 412 148 Gupta486
K0.5Na0.5NbO3 flux method 240 160 Lin487
K0.622Na0.378NbO3 top-seeded solution growth 70 161 Tian488
0.95KNN−0.05LiNbO3 Bridgman 9 185 405 Chen181
(K,Na)(Nb,Ta)O3 top-seeded solution growth 267 0.83 200 Zheng489
K0.53Na0.47Mn0.004Nb0.996Oy flux method 40 Inagaki490
K0.14Na0.86Mn0.005Nb0.995Oy flux method 37 Noguchi491
Mn-doped KNN floating zone method 106 Inagaki492
Na0.5K0.5Nb0.995Mn0.005O3 flux method 52 424 0.64 161 Inagaki490
0.5% Mn−K0.5Na0.5NbO3 flux method 730 270 Lin487
K0.5Na0.5NbO3 with B2O3 flux flux method 32 106 Saravanan493

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crystals grown by the Bridgman method possess an enhanced 1


O2 + 2Nb′Nb + V •• * *
O → OO + 2Nb Nb
piezoelectricity of ∼405 pC/N,181 which is almost two times 2 (8)
that of ceramics with the same composition.101 In addition, Lin
et al. also reported a larger d33 (∼270 pC/N) in 0.5%Mn- 1
modified K0.5Na0.5NbO3 single crystals grown by the high- V ••
O + O2 → O*O + 2h•
2 (9)
temperature solution method using a K2CO3−Na2CO3 eutectic
composition as flux,487 which is also superior to a pure KNN Nb4+ is usually found to exist in KNN single crystals,128
due to the involvement of high domain densities, as shown in leading to a high leakage current density due to the 4d electrons
Table 19. However, as far as piezoelectricity is concerned, most of this ion.552 However, the valence shift of Nb4+ to Nb5+
induced by oxidation treatment can reduce its leakage current
Table 19. Piezoelectricity of Pure and MnO2-Modified KNN density.128 It is well known that oxygen vacancies (V••O ), which
Single Crystal.487 result from the K and Na vacancies during high-temperature
processing, are involved in KNN single crystals.129,181,547,548
compositions TO−T (°C) Tc (°C) d33 (pC/N) Therefore, the leakage current density of KNN single crystals
K0.5Na0.5NbO3 208 423 160 becomes higher when they are annealed under a high-pressure
0.5% Mn−K0.5Na0.5NbO3 193 416 270 oxygen atmosphere.128 According to eq 9, the h• conduction (p
1.5% Mn−K0.5Na0.5NbO3 194 418 230 type) of oxidized KNN single crystals is generated and then
2.0% Mn−K0.5Na0.5NbO3 183 412 220 dominates the leakage behavior at room temperature. As a
result, it is necessary to decrease the formation of h• in KNN
reported results on the piezoelectric properties of KNN-based single crystals in order to further reduce its leakage
single crystals are disappointing because of the involvement of current.128,509 For example, the addition of Mn2+ is an effective
high leakage current induced by defects.128,484,487,490−492,508 way to decrease the leakage current of KNN single
It was thought that the leakage current of KNN single crystals.487,490−492 The increasing Mn valence (Mn2+−Mn4+)
crystals is controlled by the electron−hole (h•) conduction;128 can absorb h• and then realize the objective of lowering its
the formation of h• is demonstrated in eqs 8 and 9.552 leakage current when Mn2+ is used to substitute the Nb site in

Table 20. Preparation Conditions and Electrical Properties of KNN-Based Thin Films553−586

material system substrate preparation method d33 (pm/V) Pr (μC/cm2) ref


K0.5Na0.5NbO3 Pt/Ti/SiO2/Si chemical solution deposition 74.0 553
K0.5Na0.5NbO3 Pt/Ti/SiO2/Si chemical solution deposition 40 554
K0.51Na0.49NbO3 SrRuO3/SrTiO3 hydrothermal method 14 555
K0.5Na0.5NbO3 SrRuO3/SrTiO3 rf magnetron sputtering 12.05 556
K0.5Na0.5NbO3 Pt/TiOx/SiO2/Si chemical solution deposition 7 557
K, NaNbO3 Pt/TiO2/SiO2/Si sol−gel method 3.54 558
K,NaNbO3 LNO/Si rf magnetron sputtering 11.5 559
K0.5Na0.5NbO3 [110] Nb−SrTiO3 sol−gel method 45.1 17.3 560
(K,Na)NbO3 LaNiO3/Si rf magnetron sputtering 58 12 561
K0.5Na0.5NbO3 Pt/TiO2/SiO2/Si sol−gel method 8 562
K0.5Na0.5NbO3 Pt/TiOx/SiO2/Si chemical solution process 46 7 563
K0.5Na0.5NbO3 Pt/TiO2/SiO2/Si rf-magnetron sputtering 64.5 21.1 564
K0.5Na0.5NbO3 (thick film) Pt/Ti/SiO2/Si chemical solution deposition 56 12 565
K0.5Na0.5NbO3 Pt/Ti/SiO2/Si chemical solution deposition 35 9.1 566
Mn2+-K0.5Na0.5NbO3 Pt/Ti/SiO2/Si reactive template method 124* 3.05 567
K0.5Na0.5NbO3 (thick film) Pt/TiO2/Al2O3 screen printing 82.5 568
K0.5Na0.5NbO3 (thick film) platinum foils electrophoretic deposition 40 569
K0.5Na0.5NbO3 (thick film) Pt/Ti/SiO2/Si aerosol deposition method 8.1 570
(K,Na)NbO3−BaCu1/3Nb2/3O3 Pt/sapphire aerosol deposition method 110* 18.03 571
(K0.48Na0.48Li0.04)(Nb0.775Ta0.225)O3 Pt/Ti/SiO2/Si pulsed laser deposition 49 11.3 572
(Na,K)NbO3−LiTaO3 Nb−SrTiO3 hydrothermal method 25 573
0.948K0.5Na0.5NbO3−0.052LiSbO3 Pt/TiO2/Al2O3 aerosol deposition 50 15.5 574
0.94K0.52Na0.58NbO3−0.06LiNbO3 Pt/Ti/SiO2/Si sol−gel method 192 9.7 575
K0.44Na0.52Li0.04Nb0.84Ta0.1Sb0.06O3 SrRuO3/SrTiO3 pulsed laser deposition 53 576
Na0.52K0.44Li0.04Nb0.84Ta0.10Sb0.06O3 Pt/MgO pulsed laser deposition 26.3 577
K0.44Na0.52Li0.04Nb0.84Ta0.10Sb0.06O3 SrRuO3/SrTiO3 pulsed laser deposition 7.5 578
K0.48Na0.48Li0.04Nb0.895 Mn0.005Ta0.10O3 Pt/TiO2/SiO2/Si chemical solution deposition 61 16.1 579
0.92KNN−0.06BaZrO3−0.02Bi0.5Li0.5TiO3 Pt/(001)MgO pulsed laser deposition 24.5 580
K0.4425Na0.52Li0.0375Nb0.8825Sb0.08Ta0.0375O3 Pt/Ti/SiO2/Si sol−gel 9.5 581
K0.44Na0.52Li0.04Nb0.84Ta0.10Sb0.06O3 SrRuO3/SrTiO3 pulsed laser deposition 4 582
K0.44Na0.52Li0.04Nb0.84Ta0.1Sb0.06O3−Mn4+ SrRuO3/SrTiO3 pulsed laser deposition 15 583
K0.44Na0.52Li0.04Nb0.84Ta0.1Sb0.06O3−Mn SrRuO3/SrTiO3 pulsed laser deposition 10 (Ps) 584
K0.5Na0.5Nb0.8Ta0.2O3−Mn Pt/TiOx/SiO2/Si chemical solution deposition 58 7 585
0.95K0.5Na0.5NbO3−0.05CaZrO3−Mn Pt/TiOx/SiO2/Si chemical solution deposition 32 586

2579 DOI: 10.1021/cr5006809


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KNN,128,495,497,509 leading to a high remanent polarization (Pr bulk materials, it is difficult to form phase boundaries in the
≈ 40 μC/cm2). corresponding material system.575−582 In the past, researchers
4.5.7. Thin Films. Since the increase in interest in the have attempted to construct phase boundaries in KNN-based
piezoelectric activity of KNN-based ceramics, efforts have been thin films using the phase boundary compositions of the
made to prepare corresponding thin films due to their potential corresponding bulk materials,575−582 but the results are
applications for microdevices such as microelectromechanical disappointing due to a number of factors (e.g., composition
systems.552−590 However, two main issues still hinder the deviations, lattice mismatch between thin film and substrate,
fabrication of high-quality KNN-based films: (i) composition etc.). As a result, there are considerable challenges for the
deviations from stoichiometry and (ii) the loss of alkali oxides development of high-performance KNN-based thin films.
during preparation.553,573,589,590 Table 20 lists the preparation When KNN-based films are prepared, two important factors
methods and the corresponding electrical properties of KNN- (composition deviations and the loss of alkali metals) should be
based materials in the form of thin films or thick films.553−586 first considered, and other factors should also be addressed,
One can observe from Table 20 that the ferroelectric and such as preparation parameters, buffer layers, dopants, or
piezoelectric properties of KNN-based materials (e.g., thin film substitutions, etc. More importantly, much more attention
and thick film) can be promoted to varying degrees by some should be given to the design and construction of phase
methods, such as the use of stabilizing agents,553 new boundaries as well as the relationships between strain and
preparation techniques (hydrothermal method),573 excess alkali electrical properties if subsequent breakthroughs are desired.
metals,557,562 different substrates,552−586 processing condi- 4.5.8. Poling Conditions. The optimized poling conditions
tions,555,567,574 buffer layers,556,559,561,577,582 dopants or ion are a very important tool to improve the piezoelectric
substitutions,571−575,577,579−585 orientation,559−561,567,582 an- properties of lead-based or lead-free ceramics,166,169,284,510−522
nealing atmosphere,564 etc. For a pure KNN thin film,553−564 including poling temperatures, poling electric fields, dwell
some factors strongly affect their ferroelectric (Pr = 7.0−21.1 times, etc. Recently, much attention has been given to the
pm/V) and piezoelectric properties (d33* = 40−74 pm/V). For effects of the poling conditions on the electrical properties of
example, Kim et al. have shown that d33* values of 40 pm/V for lead-free ceramics, such as BaTiO3,45,512,513 Bi1/2Na1/2-
KNN thin films can be attained by doping excess K and Na,554 TiO3,513−519 and K1/2Na1/2NbO3.166,169,265,284,520−522 For
while the piezoelectric activity can be further promoted up to KNN ceramics, the poling conditions (especially poling
d33* = 56−74 pm/V by introducing stabilizing agents temperatures) become very important due to the intrinsic
(diethanolamine and ethylenediaminetetraacetic acid)553 or characteristics of the O−T phase boundary with a
polyvinylpyrrolidone565 because of the decrease of crystal- PPT.166,169,265,520−522 As far as KNN-based ceramics are
lization temperature and the suppression of the volatility of concerned, one usually chooses poling temperatures near its
alkali ions.587,588 A comparable piezoelectric constant (d33* = phase transition temperature.169,265 For example, Du et al.169
64.5 pm/V) of KNN thin films annealed under a Na2O and Wu et al.265 improved the d33 values of KNN-based
atmosphere can be also observed by different preparation ceramics by optimizing the poling temperatures (Tp), that is,
techniques (rf magnetron sputtering).564 It was found that the Tp is located at the phase transition temperatures.
different substrates also affect the ferroelectric properties of According to such a regulation, the d33 value can be increased
KNN thin films,568,570 and the Pr values of the films deposited greatly for KNN-based ceramics with O−T phase bounda-
on Nb-doped SrTiO3560 are much higher with respect to those ries.520 Morozov et al.521 also studied the influence of the
deposited on Pt/TiO2/SiO2/Si substrates,558 due to the poling temperature on the piezoelectricity of Li-, Ta-, and Mn-
involvement of the (110) orientation.560 In addition, the modified (K,Na)NbO3 ceramics with O−T phase boundaries,
effects of the orientations on ferroelectric and piezoelectric showing that the low-signal dielectric and piezoelectric
properties of a pure KNN thin film were also systematically properties in orthorhombic phase can be enhanced by poling
studied,559−561,567,582 and [110]-oriented KNN thin films were in tetragonal phase. Zhao et al.522 investigated the relationships
found to possess higher Pr values of 17.3 μC/cm2 because the between 90° domain reorientations and poling fields of
[110] orientation is its spontaneous polarization direction, (K,Na,Li)NbO3 ceramics by X-ray diffraction analysis, indicat-
while a large d33 of 50.5 pm/V can be observed in the [001]- ing that the 90° domain reorientation can be effected by
oriented materials560 due to the involvement of reversal of 180° applying poling fields (5 kV/mm), finally leading to enhanced
domains. Also, KNN-based thick films were also prepared, and piezoelectricity. Recently, Li and Wang et al.166 promoted the
their electrical properties were found to be comparable to the enhanced piezoelectricity of KNN-based ceramics from 190 to
corresponding bulk materials.568,571 For example, it is of great 324 pC/N by the aging and repoling method and proposed that
interest to note that a large d33 of 110 pm/V can be shown in both defect migration and rotation of spontaneous polarization
Ba(Cu1/3Nb2/3)O3-modified KNN thick films owing to the are responsible for such a phenomenon. Recently, we
presence of large grain sizes and abnormal grain growth,571 and investigated the effects of poling conditions on the piezo-
moreover, the KNN thick films also possess a comparable d33 to electricity of (1−x)(K 0 . 4 2 Na 0 . 5 8 )(Nb 0 . 9 6 Sb 0 . 0 4 )O 3 −
the corresponding bulk materials due to their dense micro- x(Bi0.5K0.5)0.90Zn0.10ZrO3 ceramics with R−T phase boundaries,
structure.568 Recently, Goh et al. reported a piezoelectric whereby a high d33 can be attained when Tp is located at its
constant of 25 pm/V in a 480 nm KNN thick film grown at a TR−T. A very low poling electric field (>0.8 kV/mm) was
very “low” temperature of 130 °C using a new sustainable enough to warrant full polarization due to the involvement of
hydrothermal method, which results from the decrease of the more polarization states.284 As a result, the optimization of
loss of alkali metals.573 poling conditions becomes very important for further enhance-
Although the ferroelectric and piezoelectric properties of ment of the piezoelectric activity of KNN-based ceramics and
KNN-based films can be improved by these methods,553−564 should be given further attention.
their electrical properties are still poor when compared to lead- 4.5.9. Sintering Aids and Sintering Atmosphere.
based or the corresponding bulk materials. Unlike KNN-based Sintering aids can improve the electrical properties of KNN
2580 DOI: 10.1021/cr5006809
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Table 21. Electrical Properties of KNN-Based Ceramics with Doping Oxides


material system density or relative density ε/εo d33 (pC/N) kp tan δ Qm ref
KNN−Bi2O3 99.3% 140 0.46 410 147
KNLN−CuO 4.33 g/cm3 1287 109 0.36 1023 530
KNN−CuO 98.9% 237 96 0.389 0.005 415 531
KNLNTS−Fe2O3 257 0.53 543
KNN−Fe2O3 97.5% 593 136 0.41 0.042 412 544
KNN−La2O3 93.3% 815 92 0.34 0.179 396 544
KNN−(La−Fe2O3) 96.7% 723 145 0.43 0.039 392 544
KNN−ZrO2 905 100 0.040 591
KNN−ZnO 97% 652 117 0.44 0.033 418 592
KNN−SnO2 98% 627 108 0.39 0.045 405 592
KNN−CdO 95.3% 493 107 0.42 0.040 406 592
KNN−CuNb2O6 4.47 g/cm3 92.5 0.40 1933 526
KNN−ZnO−SnO2 4.48 g/cm3 503 124 0.398 0.010 596
KNN−CuO−SnO2 97.8% 710 120 0.38 0.013 1040 597
KNNS−K4CuNb8O23−La2O3 4.376 g/cm3 160 0.38 283 593
KNN−MnO2−K5.4Cu1.3Ta10O29 4.65 g/cm3 300 90 0.40 0.003 1900 594
KNN−K5.4Cu1.3Ta10O29−CuO 97% 285 94 0.38 0.0018 3053 595

materials by the improvement in the densification and between the extrinsic factors and the piezoelectric properties of
microstructure.130,140,143,147,523−545 In recent decades, many KNN-based materials.
aids have been used to sinter KNN ceramics (refs 130, 140, 4.6.1. Density vs Electrical Properties. It is well known
143, 147, 523−546, 591, 601, and 602), including K4CuNb8O23 that densification of pure KNN ceramics is difficult due to their
(KCN), 130 K 5.4 CuTa 10 O 29 (KCT), 140,143,524 K 1.94 Zn 1.06 - poor sinterability and high volatility;3,121,127,137,249 thus, poor
Ta 5.19 O 15 (KZT), 525 CuNb 2 O 6 , 526 CuO, 145,527−531,602 d33 values are often observed by conventional solid-state
Mn3O4,532 MnO2,533,534 MoO3,535 ZnO,536−539 La2O3,540 methods.137,249 As a result, it is very important to understand
Bi2O3,147,541,542 Fe2O3,543,544 V2O5,545 and ZrO2.591 Sintering the relationships between density and piezoelectric activity of
aids have two main advantages for KNN materials: (i) KNN ceramics except for the phase boundaries,125 the
improving the density, such as KZT, KCN, etc.; and (ii) compositions,125 or other factors. Here we gave an example
enhancing electrical properties (e.g., d33, kp, Qm, etc.) due to and discussed the influence of the density on the d33 in a pure
their “softening” or “hardening” characteristics, such as CuO, KNN ceramic using different preparation methods, as shown in
KCN, KCT, etc. In addition, the electrical properties of KNN Table 22. It is clear that a pure KNN ceramic sintered in air has
materials could be improved by doping with two sintering
aids,593−597 such as K4CuNb8O23 and La2O3,593 MnO2 and Table 22. Relationship between Density and Piezoelectricity
K5.4Cu1.3Ta10O29,594 K5.4Cu1.3Ta10O29 and CuO,595 ZnO and of a Pure KNN Ceramic Obtained by Different Groups
SnO2,596 CuO and SnO2,597 etc. Table 21 shows the density relative d33
and electrical properties of KNN ceramics with doping preparation density (pC/
oxides.147,526,530,531,543,544,591−597 In particular, the ceramic material system method ρ (%) N) kp ref
matrixes used mainly involve a pure K0.5Na0.5NbO3 air sintered 4.30 95.3 110 0.39 121
KNN147,526,531,544,546,547,594−597 not those doped with other K0.5Na0.5NbO3 air sintered 4.26 94.4 80 137
components.530,543 As shown in Table 21, a higher d33 is K0.5Na0.5NbO3 air sintered 4.25 94.24 80 0.36 249
attained in the ceramics because of the improved density K0.5Na0.5NbO3 spark 4.47 >99.0 148 0.39 127
plasma
induced by the addition of oxides,147,530,542,591,593,596,597 and a sintering
higher Qm was also shown.147,526,531,542,543,546,547,593−597 In K0.5Na0.5NbO3 hot pressed 4.46 98.89 160 0.45 249
addition, the atmosphere during sintering is an important factor
to determine the electrical properties of KNN materials by
changing the microstructure (e.g., grain morphology598 and a lower density than one sintered by SPS or hot press
density599−601). Among sintering atmospheres, an oxygen methods;121,127,137,249 thus, higher d33 values are shown by SPS
atmosphere during sintering usually has a large effect on the or hot-pressed samples due to the improved density.127,249 In
electrical properties of KNN ceramics due to microstructure the past decade, some methods (e.g., sintering temper-
evolution.598−601 ature, 1 1 2 , 1 6 5 , 1 7 7 , 4 2 0 − 4 3 2 , 4 7 0 rapid sintering techni-
4.6. Extrinsic Factors que,127,447,450,451 the use of sintering aids (refs 130, 140, 143,
147, 523−545, and 602), and sintering atmosphere598−601)
In the last section, we illustrated the influences of intrinsic have been used to improve the density of KNN ceramics.
factors (i.e., crystalline structure, lattice parameters evolution, Among these methods, the main goal is to suppress the loss of
phase boundaries, etc.) and some special preparation alkali metals112,127,165,177,421−431,447,450,451,470 or the formation
techniques on the piezoelectric properties of KNN-based of liquid phases130,140,143,147,523−545 during the sintering
materials. In addition, extrinsic factors (i.e., density, micro- process. The piezoelectric activity of KNN materials can
structure evolution, domain structure, etc.) also play a crucial often be enhanced by increasing their den-
role in the development of technological applications. As a sity.127,147,249,530,542,591 However, it was also found that the
result, we briefly provide an overview of the relationships piezoelectric activity of KNN-based materials was not only
2581 DOI: 10.1021/cr5006809
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Figure 21. SEM images of KNN-based ceramics with R−T phase boundaries reported by us.110,112,115,114,117,285

dependent on the density but also very sensitive to fluctuations It was previously reported that abnormal grain growth
of composition (e.g., the degree of volatilization) when the (AGG) was usually present in KNN-based ceramics, leading to
compositions are situated at the phase boundary regions.125 As degradation of their piezoelectric proper-
a result, other factors should be also considered except for the ties.105,114,173,269,284,285,606 Recently, bimodal grain size distri-
density. bution has also been observed in KNN-based ceramics with R−
4.6.2. Grain Morphology vs Electrical Properties. It is T phase coexistence108−118,285 (see Figure 21). However, a
usually accepted that the microstructure (e.g., grain morphol- large d33 of >400 pC/N can be attained, which seems to be at
ogy) of KNN-based materials can be modulated by a sintering odds with the reported results.105,173 For KNN-based ceramics
aid,130,140,143,147,523−545 the use of new preparation techni- with R−T phase boundaries, the phase boundary should play a
ques,127,249,447,450,451 various sintering atmospheres,598 and critical role in the piezoelectric properties of KNN-based
others. Many researchers have improved the sinterability of ceramics; thus, the negative effect of AGG can be almost
KNN-based materials using different sintering neglected or decreased. As a result, the piezoelectric activity of
aids145,413,528,533,534,537,539,604 (e.g., CuO,145,413,528 NiO,603 KNN-based materials was more sensitive to the phase boundary
ZnO,537,539 MnO,604 and MnO2533), and the existence of A- with respect to the negative effect of AGG when the
site vacancies can offset the formation of the hygroscopic compositions were situated at the R−T phase boundary
secondary phases because these chemical elements substitute regions.108−118,285 Preparation of R−T KNN-based ceramics
the B site in ABO3.124 In addition, sintering aids are often used with a unimodal grain size distribution is necessary in order to
to densify KNN ceramics by introducing a liquid further promote their piezoelectric activity. Some methods may
phase 130,140,145,143,147,523−545 or a “transient” liquid decrease the extent of AGG in KNN materials, such as the
phase,124,132,537 and the grain morphologies can be also particle size (nanopowder) of calcined powders, milling
controlled by changing the concentration of sintering strategies, etc.607
aids.124,132,537 In particular, bimodal grain size distributions Recently, it was shown that grain morphologies can be
were often observed in KNN-based ceramics doped by controlled by developing KNN-based low-dimensional materi-
oxides.132,539 It was proposed that the general grain growths als using different preparation techniques,271,608−613 strongly
observed in oxide-doped samples should be attributed to affecting their electrical properties.271,610−613 For example, Li et
enhanced atomic mobility,132,539 dramatic grain growth can be al. reported that one-dimensional KNN nanorods fabricated by
induced by the difference in surface free energies between large a molten-salt method possess a high piezoelectric constant
grains and small grains,3 and then bimodal grain sizes can be (d33* ≈ 230 pm/V),612 the K/Na ratios of one-dimensional
facilitated and accelerated due to the presence of a liquid phase. KNN nanorods seriously affect their piezoelectricity, and
However, piezoelectric activity will usually be degraded by the moreover the phase boundary is also obviously different from
addition of sintering aids because a material’s phase transition that of KNN bulk.271 In addition, higher d33* values of 180 pm/
temperature deviates to room temperature.145,537,413,603,604 In V were also shown in vertically aligned lead-free (K0.6Na0.4)-
addition, the piezoelectric activity of KNN-based ceramics is NbO3 nanorod arrays via the facile hydrothermal method.613
closely related to their average grain sizes.132,605 Also, the grain Thus, control of morphology is an efficient way to promote the
growth behavior of a pure KNN ceramic can be controlled by piezoelectric properties of KNN-based materials.271,610−613
different sintering atmospheres because of the critical driving 4.6.3. Domain Structure vs Electrical Properties.
force for 2D nucleation-controlled grain growth caused by their Domain structure can determine the piezoelectric properties
different edge free energies.598 As a result, the grain of a ferroelectric material,446,268,269,406,614−622 that is, the
morphologies of KNN-based ceramics can be modified by electrical properties of a ferroelectric material can be modulated
different methods. by changing the domain structure as well as domain−wall
2582 DOI: 10.1021/cr5006809
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Figure 22. (a) Relationship between phase boundary type, piezoelectric constant, and Curie temperature,12,90−201 and (b) comparison of the
piezoelectric properties of PZT and KNN.

rotations. As a result, it is necessary to clarify the ferroelectric the disappearance of the polar anisotropy by means of
domain structure of KNN-based materials with the phase transmission electron microscopy, which also confirms the
boundary compositions in order to further understand its different domain structure between PPT and MPB,268 and the
nanoscale properties and improve its piezoelectricity. R−T phase boundary is also confirmed by the tweed-like
The domain structure of KNN-based materials can be well domain morphology.619 In addition, the relationships between
identified by a number of measurement techniques (see section domain patterns and time-aging stability of d33 were illuminated
3). For example, the domain patterns concerning 60° and 90° in (K0.5Na0.5)1−xLixNbO3 ceramics, and the involved 180°
domain walls were observed in pure or Mn-doped KNN single domains cause the degradation and time-aging instability of
crystals by polarizing optical microscopy, and the domain width piezoelectric properties.620 It was also found that domain size
was found to be a few tens of micrometers.614 The unpoled seriously affects the electrical properties of KNN-based
KNN ceramics possess only 90° and 180° domain walls,269 materials. For example, the decreased domain sizes can reduce
while the domain structure changes when Li is doped to KNN, the coercive field of Li0.02(K0.45Na0.55)0.98NbO3 ceramics,621 and
that is, the domains (e.g., 60°, 90°, and 180°) and S-type both curved domain stripes and larger average domain width
domain walls were simultaneously observed in a grain.615 In were found to improve the piezoelectric properties of
addition, some researchers have investigated the domain (K0.5Na0.5)0.965Li0.035(Nb0.8Ta0.2)O3 ceramics with O−T phase
structure of KNN-based materials with the phase boundary coexistence.622 As a result, the evolutions of the piezoelectric
compositions.406,616 For example, the phase transition temper- properties can be described and explained by characterizing
atures (e.g., TR−O, TO−T, and TC) of KNN single crystals were their domain structure, and correspondingly the piezoelectricity
graphically confirmed by the changes of the domain structures can be promoted by varying the domain types and sizes.
under different temperatures.406 The coexisting tetragonal and In this section, the electrical properties of KNN-based
orthorhombic domains were vividly observed in one grain of materials could be further improved by microstructure variation
K0.44Na0.52Li0.04Nb0.86Ta0.1Sb0.04O3 by piezoresponse force using tools besides the phase boundary. Among those tools,
microscopy, providing a basis for the understanding of the their electrical properties can best be improved by controlling
PPT of KNN-based materials.616 As a result, the domain the microstructure evolution (e.g., density, grain size and
structure can allow the characterization of the phase structure morphology, domain structure, etc.). In addition, multiple tools
of KNN-based materials. are always used together to modify the KNN-based materials.
There is a close relationship between domain structure and As a result, more consideration should be given to these
phase structure of KNN-based materials, and the phase supplementary tools for preparing KNN materials.
structure can determine its piezoelectric activity.268,617−622 As
a result, the piezoelectric properties of KNN-based materials 5. RELATIONSHIP BETWEEN PHASE BOUNDARIES
can be tailored by varying their domain structure. Recently, the AND PIEZOELECTRICITY
relationships between domain structure and piezoelectricity of Generally speaking, the piezoelectric activity of KNN-based
KNN-based materials have been studied by considering the ceramics can be enhanced in different degrees by constructing
changes in domain structure. Zhang et al.617 investigated the phase boundaries and modifying the microstructure of a
evolution of domain structure in hot-pressed KNN ceramics material, while its piezoelectric activity is strongly sensitive to
before and after poling, and the irreversible domain wall the phase boundary types. In this section, we further clarify the
motions were found to strongly contribute to the piezoelectric relationships between phase boundary and piezoelectric activity
coefficient of the hot-pressed KNN ceramics. Transmission of KNN-based materials, addressing the weakness and the
electron microscopy was used to in situ identify the evolutions corresponding solution methods. Tables 1−12 display the
of the domain morphologies and phase structures under driving influences of the phase boundary types on the piezoelectric
electric fields (E) of 0.948(K0.5Na0.5)NbO3−0.052LiSbO3, and activity of KNN-based materials. There is a progressive
it was found that the enhanced piezoelectric properties result development from O−T, to R−O, to R−T in chronological
from a tilted monoclinic phase from O−T for E > 14 kV/cm.618 order, and the trend of d33 is R−O < O−T ≤ R−T according to
For O−T (Na,K,Li)(Nb,Ta,Sb)O3 ceramics, the nanodomains the piezoelectric activity, as shown in Tables 1−12. At the same
(e.g., 20−50 nm width) generated enhanced piezoelectric time, it is much more difficult and complicated to construct R−
properties due to the reduced domain wall energy induced by T phase boundaries with respect to R−O and O−T, as the R−
2583 DOI: 10.1021/cr5006809
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Figure 23. (a) Articles concerned with lead-free piezoelectric materials in refereed journals published between 2010 and 2014 obtained from ISI Web
of Science using the keywords “lead-free piezoelectric” and “strain”. (b) Relative amounts of several kinds of lead-free piezoelectric materials in strain
investigations.

T phase boundary can be only formed by adding two or more 6.1. Piezoelectric Energy Harvesting
additives.106−113,256,277,284,285 In addition, the interrelationships So-called “energy harvesting” devices have attracted much
among different phase boundary types were also established, attention because energy can be generated from renewable
and the methods to construct the R−O and O−T phase sources (e.g. temperature, vibration, air flow, etc.), with the
boundaries provide a solid practical and theoretical basis for hope of solving the energy crisis if these devices can be
designing the corresponding R−T, that is, the R−T phase developed and made practical.623,624 Among these energy
boundary can be induced by combining two kinds of harvesting devices, piezoelectric energy harvesting devices can
boundaries (R−O and O−T) using the optimum additives. convert mechanical energy into electrical energy; moreover,
Figure 22a shows the piezoelectric constant, phase boundary their energy density is usually superior to other energy
types, and Curie temperature of KNN-based ceramics, as devices.625−628 Since piezoelectric nanogenerators fabricated
collected from a number of studies (refs 12, 17, 97, 101, 102, by piezoelectric zinc oxide nanowire arrays were first reported
104, 106−118, 166, 201, and 266−285). The types of phase for the direct energy conversion from mechanical motion to
boundaries strongly affect the d33 value of KNN materials: R− electrical power,624 much attention has been focused on
O ceramics possess a poorer d33 with respect to those with R− investigations into piezoelectric energy harvesting devices. In
T and O−T, the O−T ceramics have a wide d33 distribution the past, most piezoelectric energy harvesting devices were
from 200 to 350 pC/N, and a large d33 of >330 pC/N is usually fabricated using PZT-based materials due to their promising
induced in R−T ceramics. In addition, it was also found that electrical properties.625,626,628,629 Recently, energy harvesting
the piezoelectric activity of R−T KNN-based ceramics can be devices have been fabricated using KNN-based materials,630−632
comparable to part-PZT ceramics. However, during the motivated by environmental concerns over lead-containing
development of KNN-based materials a general trend has PZT-based materials.625,626,628,629 For example, energy harvest-
emerged whereby the d33 value is enhanced by sacrificing a ing devices based on (K0.5Na0.5)0.97(Nb0.96Sb0.04)O3 ceramics
material’s TC, and the ceramics with a large d33 (>330 pC/N) doped with 0.2 wt % CeO2 were fabricated, possessing
always have a low TC (<300 °C). As a result, the application optimum output voltage (24.6 mVrms) and power (0.839
temperature range of KNN-based ceramics should be μW) under an external vibration acceleration of 0.7 g.630 More
considered when the phase boundaries are constructed, and it recently, a large-area nanocomposite generator device was
fabricated using alkaline niobate-based particles and copper
is necessary to choose additives that increaseor at least do
nanorod fillers, providing a maximum output of up to 140 V
not significantly reduceTC.108,109 We also compared KNN
and 8 μA (∼0.5 mW).632
with PZT in terms of their d33 and TC, as shown in Figure 22b.
For TC > 200 °C, the d33 of KNN-based ceramics has been 6.2. Piezoelectric Actuator
comparable or even superior to PZT-based ceramics. As a It is well known that actuator applications require electro-
result, we believe that KNN-based lead-free piezoceramics can mechanical coupling providing high strain with high force, and
replace PZT in some applications. this requirement can be realized by piezoelectric materials that
allow direct conversion between electrical and mechanical
6. APPLICATIONS OF KNN-BASED MATERIALS energy.17,120 Currently, the piezoactuator markets were
dominated by PZT materials in the form of the ceramics or
The excellent piezoelectric properties of KNN-based materials thin films,633 and lead-free piezoelectric materials concerning
result in some practical applications (e.g., piezoelectric energy strain are also experiencing gradual growth due to environ-
harvesting, piezoelectric actuators, etc.), similar to PZT mental regulations,12,66−68,93,162,178,634 as shown in Figure 23a.
ceramics. In this section, we pay special attention to their Recently, strain investigations have triggered strong interest in
applications in the field of piezoelectric energy harvesting and the field of lead-free piezoelectrics,12,66−68,93,162,178,634 since a
piezoelectric actuators because this review mainly concerns the high unipolar strain value of ∼0.45% was first reported in BNT-
relationships between phase boundary types and piezo- based ceramics under a high driving electric field of ∼8 kV/
electricity. In addition, other practical applications are also mm.68,634 It is thought that, for the first time, the electrical
briefly mentioned.17,120 properties (strain) of lead-free piezoelectrics have become
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Figure 24. Unipolar strain in 0.965K0.45Na0.55Nb0.98Sb0.02O3−0.035Bi0.5Na0.5Zr0.85Hf0.15O3 ceramics, measured at 10 Hz and room temperature.

superior or comparable to those of lead-based examples.68,634 7. OUTLOOK AND FUTURE WORK


We can see from Figure 23b that most research has focused on We systematically reviewed the construction of phase
strain investigations with BNT-based materials because of its boundaries as well as the related physical mechanisms in
high strain values. However, issues related to their transfer into KNN-based materials by comprehensively analyzing the recent
practical applications need to be resolved despite a high strain advances in the field as well as the achieved results. Although
in the mentioned ceramics,635 that is, a high driving electric the piezoelectric activity of KNN-based materials can be
field is often required to warrant a large strain,68,634 and the promoted by constructing different phase boundaries as well as
strain hysteresis exhibits a strong nonlinearity.68,634 other supplementary tools, some issues still need to be
Recent research results show that KNN-based ceramics can addressed before large-scale application can be realized.
effectively address two of these issues,93,162,178,265,270,278,285,636 According to our review of the recent advances in KNN-
where a slimmer strain hysteresis and a relatively high unipolar based materials, a number of recurring problems haunt
researchers in the field, e.g., how to design new phase
strain value under a low driving electric field can be
boundaries, identify the phase compositions, investigate the
attained.93,162,178,265,270,278,285,636 In addition, a high unipolar interrelationships between different phase boundary types,
strain was also observed in KNN-based materials.93,178,270,278 In phase compositions, and piezoelectric properties, etc. In order
our group, 0.965K0.45Na0.55Nb0.98Sb0.02O3− to clearly solve these issues, future work will most likely focus
0.035Bi0.5Na0.5Zr0.85Hf0.15O3 ceramic systems have been on the following challenges.
recently developed (see Figure 24), and a high unipolar strain 7.1. Designing New Phase Boundaries
and a slimmer strain hysteresis compared with the BNT-based
Although the R−T phase boundary of KNN-based materials
materials68,634,635 can be simultaneously observed, due to the
can more significantly improve the piezoelectric activity with
involvement of phase boundaries, as shown in Figure 24. There respect to other phase boundary types, its piezoelectric activity
are few reports of such a high unipolar strain value in KNN- continues to catch up to those of PZT ceramics in terms of
based ceramics, which is two times as high as those reported for meeting the requirements of different applications. As a result,
(Li, Ta, Sb)-doped KNN textured ceramics.12 Recently, Li et it is necessary to further increase the piezoelectric activity of
al.636 reported that the unipolar strain of CaZrO3 and MnO2 such materials by developing new phase boundaries similar to
comodified (K,Na,Li)(Nb,Ta)O3 ceramics shows fatigue-free those of PZT.
(only small degradation within 3%) during 107 cycles under a 7.2. Analyzing Phase Compositions
field amplitude of 2 kV/mm, which results from the “softening” Phase composition identification is critical to establishing the
effect. Rubio-Marcos et al.93 developed a high strain value with relationships between phase boundaries and piezoelectric
Smax as high as 0.17% at 3 kV mm−1 in the (K0.44Na0.52Li0.04) properties, providing us with a guide to refining the phase
(Nb0.86Ta0.10Sb0.04)O3 microfiber ceramics. These results boundaries and further promoting a material’s piezoelectricity.
indicate that KNN-based materials are the most promising In addition, the relationships between domains and phase
candidates in the field of lead-free piezoelectric actua- boundaries should be established; then the piezoelectric activity
tors.265,270,278,285,636 can be modified by varying the domain structure.
In the past, transducers,148,637,638 buzzers,159,639 surface 7.3. Physical Origin of High Piezoelectricity
acoustic wave filters,640 and other devices have been developed It is very important to understand the physical origin of high
using KNN-based materials. In addition, the performance of piezoelectricity in order to investigate the relationships between
some devices is comparable to those fabricated by PZT-based the phase boundaries, phase compositions, and piezoelectric
materials. For a detailed introduction of applications, the reader properties of KNN materials. The different phase boundaries
is referred to recent works reported by Rödel and Jo.17,120 can be constructed by doping additives, then the phase
2585 DOI: 10.1021/cr5006809
Chem. Rev. 2015, 115, 2559−2595
Chemical Reviews Review

compositions concerning phase boundaries can be optimized Jiagang Wu received his B.S. degree from Sichuan University in 2003
by refining the types and concentration of the additives, and and Ph.D. degree from Sichuan University in 2008 and worked as a
finally the piezoelectric activity can be enhanced by modifying Singapore Millennium Postdoctoral Fellow (SMF-PDF) at the
the phase compositions. National University of Singapore from 2008 to 2010 (2 years). He
7.4. Intrinsic Characteristics of Phase Boundaries has been an Associate Professor at the Department of Materials
Science, Sichuan University, since 2011. His main research interest is
The intrinsic differences between different phase boundary
composition design and property modification of ferroelectric/
types (e.g., O−T, R−O, R−T, etc.) and the intrinsic
piezoelectric/multiferroic materials.
characteristics of MPB and PPT were studied by investigating
the temperature-dependent domain structure.
7.5. Investigating the Stability of Piezoelectricity
The greatest challenge for KNN-based materials is how to
improve the stability of piezoelectricity. In the past, there was
conflict between piezoelectricity and its stability, that is, if a
large d33 induced by PPT phase boundaries shows strong
temperature dependence. As a result, phase boundaries with
MPB characteristics may be an effective way to solve this issue.
It is still an open question as to whether KNN-based materials
possess phase boundaries with MPB characteristics.
7.6. Other Issues
Potassium−sodium niobate lead-free piezoceramics will be a
promising lead-free materials for actuator applications. It was
wondered whether a large strain can be induced by phase Dingquan Xiao received his B.S. degree from Sichuan University in
transitions. As a result, it may be very interesting to investigate 1968 and M.S. degree from Sichuan University in 1980, studied at the
the relationships between phase transitions and strains of Queen Mary University of London from 1980 to 1982, and worked a
potassium−sodium niobate materials. senior visiting scholar at the University of Pennsylvania in 1990 and
the University of Houston in 1998. He has worked at Sichuan
8. CONCLUSIONS University since 1983. Currently, he is a Professor in the College of
High-performance lead-free piezoceramics have become an Materials Science and Engineering of Sichuan University. His main
international research frontier in the fields of high technology research interests include ferroelectric/piezoelectric ceramics, dielec-
and new materials. In this review, we systematically reviewed tric materials, ferroelectric thin films, ecomaterials, and electrochemical
the developments of phase boundaries as well as the techniques. He is a member of the Chinese Materials Research Society
piezoelectric properties of KNN-based materials, and some and the Chinese Physics Society.
suggestions for the future development of KNN materials were
also addressed. In the past decade, piezoelectric properties have
been greatly increased by constructing phase boundaries, and
piezoelectricity comparable to those of PZT-based materials has
been achieved. As a result, we believe that KNN-based lead-free
ceramics will gain wide practical application in the near future.

AUTHOR INFORMATION
Corresponding Author
*E-mail:wujiagang0208@163.com and msewujg@scu.edu.cn.
Notes
The authors declare no competing financial interest.
Biographies
Jianguo Zhu received his M.S. degree from Sichuan University in 1987
and Ph.D. degree in materials science from Sichuan University in 1998.
He has worked at Sichuan University since 1987. Currently, he is
Professor and Dean of the College of Materials Science and
Engineering of Sichuan University. His research activities are
ferroelectric/piezoelectric ceramics, dielectric materials, and ferro-
electric thin films. He is a member of the Chinese Materials Research
Society and the Sichuan Silicate Society.

ACKNOWLEDGMENTS
We gratefully acknowledge the support of the National Science
Foundation of China (NSFC Nos. 51102173, 51272164,
51332003, and 51472169), the Fundamental Research Funds
for the Central Universities (2012SCU04A01), introduction of
2586 DOI: 10.1021/cr5006809
Chem. Rev. 2015, 115, 2559−2595
Chemical Reviews Review

talent starting funds of Sichuan University (2082204144033), (27) Solid Waste: Hazardous Electronic Waste, U.S. California
and the College of Materials Science and Engineering of Senate Bill No. 20, 2003.
Sichuan University. We are also thankful to a number of (28) Solid Waste: Hazardous Electronic Waste, U.S. California
researchers who provided help during our research: Xiaojie Lou Senate Bill No. 50, 2004.
(29) Restriction of the Use of Certain Hazardous Substances in
and Xiangjian Wang (Xi’an Jiaotong University), Hui Wang
Electrical and Electronic Equipment, Ministry of Environment and
(Sichuan University), Ruishi Xie (Southwest University of Forestry Turkey Regulation No. 26891, 2008.
Science and Technology) and Hao Tian (Harbin Institute of (30) Act for Resource Recycling of Electrical and Electronic
Technology). Finally, we would like to sincerely thank the Equipment and Vehicles, Environment and Labor Committee of the
reviewers for valuable suggestions. National Assembly of Korea Bill No. 6319, 2007.
(31) Law for Promotion of Effective Utilization of Resources,
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2595 DOI: 10.1021/cr5006809


Chem. Rev. 2015, 115, 2559−2595